WO2023157792A1 - トナー - Google Patents

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Publication number
WO2023157792A1
WO2023157792A1 PCT/JP2023/004728 JP2023004728W WO2023157792A1 WO 2023157792 A1 WO2023157792 A1 WO 2023157792A1 JP 2023004728 W JP2023004728 W JP 2023004728W WO 2023157792 A1 WO2023157792 A1 WO 2023157792A1
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WIPO (PCT)
Prior art keywords
toner
tan
mass
less
parts
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PCT/JP2023/004728
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English (en)
French (fr)
Japanese (ja)
Inventor
浩二朗 赤▲崎▼
康平 山田
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Zeon Corp
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Zeon Corp
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Priority to US18/837,233 priority Critical patent/US20250147442A1/en
Priority to EP23756317.6A priority patent/EP4481501A4/en
Priority to JP2024501359A priority patent/JPWO2023157792A1/ja
Priority to CN202380021235.6A priority patent/CN118742861A/zh
Publication of WO2023157792A1 publication Critical patent/WO2023157792A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08782—Waxes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09783—Organo-metallic compounds
    • G03G9/09791—Metallic soaps of higher carboxylic acids

Definitions

  • the present disclosure relates to toners used for developing electrostatic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like.
  • image forming apparatuses such as electrophotographic apparatuses, electrostatic recording apparatuses, and electrostatic printing apparatuses
  • an electrostatic latent image formed on a photoreceptor is developed with toner, and the toner image is transferred onto a transfer material such as paper. After that, a fixed image is formed by fixing by heating or the like.
  • a transfer material such as paper.
  • a fixed image is formed by fixing by heating or the like.
  • an image forming apparatus there is a demand for an image forming apparatus capable of achieving high image quality and high speed printing.
  • attempts have been made to develop a toner that focuses on the viscoelasticity of the toner.
  • the glass transition temperature (Tg) satisfies 45 ° C. ⁇ Tg (° C.) ⁇ 100 ° C.
  • tan ⁇ (45 ° C.) and tan ⁇ (Tg) Toners are disclosed in which the slope of a straight line through tan ⁇ (100° C.) and tan ⁇ (130° C.) are within specified ranges.
  • Patent Document 2 as external additives, first and second silica fine particles having a specific number average primary particle size and a specific triboelectric charge amount, and fatty acid metal salt particles, are contained in specific amounts.
  • a chargeable electrostatic image developing toner is disclosed.
  • Patent Document 3 in a toner used in an image forming apparatus having a cleaning brush but not a cleaning blade, fatty acid metal salt particles having a water-soluble polymer attached to the surface thereof are used as an external additive to obtain toner. It is described that contamination inside the image forming apparatus is improved by preventing the blowout.
  • Patent Document 4 as an external additive, a combination of silica particles having a specific number average particle diameter and having a hydrophobic surface and silicone resin particles having a specific number average particle diameter and porosity is contained. A toner is disclosed.
  • Toners capable of forming high-quality images are required to have both low-temperature fixability and storage stability in a well-balanced manner.
  • toner with improved low-temperature fixability tends to be more likely to squirt from the developing roller. Therefore, there is a demand for a toner that is excellent in low-temperature fixability, has good storage stability, and can suppress the occurrence of squirt. .
  • the toner tends to be ejected under high temperature and high humidity, and the toner disclosed in Patent Documents 1 to 4 suppresses the ejection of toner when continuous printing is performed under high temperature and high humidity. is difficult. Further, the toners disclosed in Patent Documents 2 to 4 also have a problem that the low-temperature fixability or storage stability tends to be insufficient.
  • An object of the present disclosure is to provide a toner that has an excellent balance between low-temperature fixability and storage stability, and that can suppress the occurrence of blow-out during continuous printing under high-temperature, high-humidity conditions.
  • the present inventors found that by controlling the viscoelasticity of the toner, the value of bulk density after conditioning determined using a powder fluidity analyzer, and the value of fluidity, Furthermore, the inventors have found that a toner can be obtained that has an excellent balance between low-temperature fixability and storage stability, and that can suppress the occurrence of blow-out during continuous printing under high-temperature and high-humidity conditions, leading to the first toner of the present disclosure.
  • the first toner of the present disclosure is a toner containing colored resin particles containing a binder resin, a coloring agent, a softening agent and a charge control agent, and an external additive
  • the glass transition temperature (Tg) specified from the temperature dependence curve of the loss tangent (tan ⁇ ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz is 65.0° C. ⁇ Tg (° C.) ⁇ 75.0 fill °C
  • Tg glass transition temperature
  • the bulk density after conditioning obtained using a powder fluidity analyzer is 0.527 g / mL or more and 0.550 g / mL or less, It is characterized by a fluidity of 80% or more.
  • the inventors of the present invention conducted intensive studies to achieve the above object, and found that low-temperature fixation can be achieved by setting the viscoelasticity of the toner and the ratio of the blow-off charge amount of the toner measured by a specific method to within a specific range.
  • the present inventors have found that it is possible to obtain a toner that has an excellent balance between properties and storage stability and that can suppress the occurrence of blowout when continuous printing is performed under high temperature and high humidity conditions, leading to the second toner of the present disclosure.
  • the second toner of the present disclosure is a toner containing colored resin particles containing a binder resin, a coloring agent, a softening agent and a charge control agent, and an external additive, containing fatty acid metal salt particles as the external additive
  • Tg glass transition temperature specified from the temperature dependence curve of the loss tangent (tan ⁇ ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz is 65.0° C. ⁇ Tg (° C.) ⁇ 75.0 fill °C
  • Tg glass transition temperature
  • the ratio of the blow-off charge amount of the toner after 1800 seconds of agitation to the blow-off charge amount of the toner after 180 seconds of agitation, measured by the following charge amount measurement method, is 0.50 or more and 1.00 or less.
  • 0.2 g of a mixture of the above ferrite carrier and the above ferrite carrier is placed in a Faraday cage, and is blown off for 30 seconds under the condition of a nitrogen gas pressure of 0.098 MPa using a blow-off powder charge amount measuring device to measure the blow-off charge amount of the toner ( ⁇ C /g).
  • toner that has an excellent balance between low-temperature fixability and storage stability, and that can suppress the occurrence of blow-out during continuous printing under high-temperature, high-humidity conditions.
  • FIG. 1 is a diagram showing a temperature dependence curve of the loss tangent (tan ⁇ ) of the toner of Example I-1 (same as the toner of Example II-1).
  • the first toner of the present disclosure is a toner containing colored resin particles containing a binder resin, a coloring agent, a softening agent and a charge control agent, and an external additive
  • the glass transition temperature (Tg) specified from the temperature dependence curve of the loss tangent (tan ⁇ ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz is 65.0° C. ⁇ Tg (° C.) ⁇ 75.0 fill °C
  • Tg glass transition temperature
  • the bulk density after conditioning obtained using a powder fluidity analyzer is 0.527 g / mL or more and 0.550 g / mL or less, It is characterized by a fluidity of 80% or more.
  • the first toner of the present disclosure has a glass transition temperature (Tg) of 65.0° C. or higher and 75.0° C. or lower, which is specified from a loss tangent (tan ⁇ ) temperature dependence curve, and a loss tangent (tan ⁇ ) of
  • Tg glass transition temperature
  • tan ⁇ loss tangent
  • tan ⁇ loss tangent
  • tan ⁇ loss tangent
  • the area of the trapezoid specified from the temperature dependence curve has a specific viscoelasticity of 35.0 or more and 48.0 or less
  • the bulk density after conditioning obtained using a powder fluidity analyzer (Conditioned Bulk Density; hereinafter sometimes referred to as CBD) is 0.527 g / mL or more and 0.550 g / mL or less, and the fluidity is 80% or more, so that both low temperature fixability and storage stability is improved in a well-balanced manner and ejection is suppressed during endurance under high temperature and high humidity conditions
  • the ejection of toner is caused, for example, by local application of heat due to the sliding of the developing roller to the toner that has accumulated near the blade portion or seal portion of the cartridge, causing the accumulated toner to fuse and form aggregates. It occurs when the aggregate melts and the toner spills from the developing roller.
  • the fluidity of the toner is reduced due to moisture absorption, and the heat applied to the toner is increased at a high temperature, so the toner tends to blow out.
  • toner does not suddenly deform when it reaches a certain temperature during fixing and storage, but gradually deforms as the temperature rises or as time elapses when held at a certain temperature. .
  • the present inventors have found that the toner has a good balance between low-temperature fixability and storage stability, and the characteristics of the toner that easily suppresses the occurrence of blowout is the glass transition temperature, which is specified from the temperature-tan ⁇ curve. (Tg) and the area of the trapezoid, and furthermore, by controlling the CBD and fluidity of the toner, it was found that the blowout of the toner can be suppressed even during high-temperature, high-humidity durability.
  • the low-temperature fixability and storage stability can be improved in a well-balanced manner. If the Tg of the toner is too high or the area of the trapezoid is too small, the low-temperature fixability tends to be insufficient, and if the Tg of the toner is too low or the area of the trapezoid is too large, blocking tends to occur during storage. It tends to become inadequate in storage stability.
  • the trapezoidal area specified from the temperature-tan ⁇ curve is obtained by simply calculating the integral of the viscosity term from the glass transition temperature (Tg) of the toner to 100°C.
  • the area of the trapezoid can also be used as an indicator of the ease of aggregation of the toner when the toner pool is formed.
  • the toner having a trapezoidal area of 35.0 or more and 48.0 or less is hard to aggregate even if it stays.
  • the CBD can be an indicator of the firmness of the toner pool (ie, the firmness of the toner mass). The smaller the CBD, the easier it is for the toner to collapse even if it stays, so the toner is less likely to agglomerate. On the other hand, if the CBD is too small, toner leakage easily occurs from the toner pool.
  • the first toner of the present disclosure has a fluidity of 80% or more, and the fluidity is sufficiently high. Therefore, in the first toner of the present disclosure, the Tg and the area of the trapezoid specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz are within the specified ranges, and the CBD value and the fluidity value are adjusted to the above-mentioned values. By controlling as described above, the toner has an excellent balance of low-temperature fixability and storage stability, and the toner does not easily stagnate.
  • the characteristics of the first toner of the present disclosure, the manufacturing method and colored resin particles of the colored resin particles used in the first toner of the present disclosure, the external additive and the external additive used in the first toner of the present disclosure are described.
  • the addition treatment method and the performance of the first toner of the present disclosure will be described in order.
  • "to" in a numerical range means to include the numerical values before and after it as lower and upper limits.
  • the first toner of the present disclosure has a glass transition temperature (Tg) of 65.0° C. ⁇ Tg, which is specified from a temperature dependence curve of loss tangent (tan ⁇ ) obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz. (°C) ⁇ 75.0°C, the area of the trapezoid with the value of tan ⁇ (100°C) as the upper base, the value of tan ⁇ (Tg) as the lower base, and the value of 100-Tg as the height is 35.0 or more 48.0 or less.
  • the loss tangent (tan ⁇ ) is defined as the ratio (G''/G') of the storage modulus (G') and the loss modulus (G'') measured by dynamic viscoelasticity measurement. It is.
  • the linearity of the temperature-tan ⁇ curve at a measurement frequency of 24 Hz within the range of 45° C. or more and 190° C. or less may have the following characteristics, for example. That is, it has one peak in the range of 65.0 ° C. or higher and 75.0 ° C. or lower, and when the temperature at which tan ⁇ of the peak reaches the maximum value is exceeded, tan ⁇ decreases and reaches the minimum value as the temperature rises. , tan ⁇ gradually increases as the temperature further increases from the minimum value, and then becomes a substantially constant value above a certain temperature.
  • dynamic viscoelasticity measurements are performed using a rotating plate rheometer (ARES-G2, manufactured by TA Instruments) using a parallel plate or crosshatch plate under the following conditions.
  • Frequency 24Hz
  • Sample set A test piece (2 to 4 mm thick) is sandwiched between 8 mm ⁇ plates with a load of 20 g, the temperature is raised to 80 ° C. and the test piece is fused to the jig, then returned to 45 ° C. and the temperature rise is started.
  • the test piece is prepared by, for example, pouring 0.2 g of the toner of the present disclosure into a cylindrical molding device of 8 mm ⁇ and pressurizing it at 1.0 MPa for 30 seconds to form a cylindrical molding with a thickness of 2 to 4 mm and 8 mm ⁇ . can do.
  • the value of tan ⁇ is rounded to the second decimal place according to Rule B of JIS Z8401:1999.
  • the value of each tan ⁇ used for calculating the area of the trapezoid is also rounded to the second decimal place.
  • the value of 100-Tg used to calculate the area of the trapezoid is rounded to the first decimal place, and the value of the area of the trapezoid is rounded to the first decimal place.
  • the glass transition temperature (Tg) specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz is the temperature dependence curve of the toner loss tangent (tan ⁇ ) obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz. is specified as the lowest temperature at which tan ⁇ becomes the maximum value in the lowest peak among the one or more peaks in the temperature region exceeding 45°C. Fine vertical fluctuations derived from measurements such as noise are not interpreted as the peaks.
  • the first toner of the present disclosure has a glass transition temperature (Tg) of 65.0° C. or higher, which is specified from a temperature-tan ⁇ curve at a measurement frequency of 24 Hz, thereby suppressing a rapid decrease in elasticity at low temperatures. Further, when the area of the trapezoid is 48.0 or less, aggregation of the toner is suppressed, so that blocking can be suppressed and the toner can be improved in storage stability. In addition, the first toner of the present disclosure has a glass transition temperature (Tg) of 75.0° C. or less, which is specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz.
  • the Tg may be 77° C. or less, but when 65.0° C. ⁇ Tg(° C.) ⁇ 75.0° C., the area of the trapezoid is 35.0 to 48.0° C. It tends to be within the range of 0 or less. If the area of the trapezoid is too large, the toner tends to aggregate when the toner stays, and the toner tends to blow out. However, the area of the trapezoid is 35.0 to 48.0.
  • the glass transition temperature (Tg) is preferably 67.0° C. or higher, more preferably 69.0° C. or higher, and is preferably 73.0° C. or lower, more preferably 71.0° C. or lower.
  • the area of the trapezoid is preferably 37.0 or more, more preferably 39.0 or more, and is preferably 46.0 or less, more preferably 45.0 or less.
  • the upper base of the trapezoid ABCD is the line segment AD, the lower base is the line segment BC, and the height is the distance of the line segment CD.
  • the area of the trapezoid ABCD is a general formula for calculating the area of a trapezoid using the value of tan ⁇ (100 ° C) as the upper base, the value of tan ⁇ (Tg) as the lower base, and the value of 100-Tg as the height It is calculated by "(upper base + lower base) x height/2".
  • the value of 100 ⁇ Tg is the difference between 100° C. and Tg (° C.), but since it is considered as the height when calculating the area of the trapezoid, it has no units.
  • the toner of the first present disclosure has a tan ⁇ (Tg) of preferably 1.50 or more, more preferably 1.60 or more, still more preferably 1.70 or more, and preferably 2.60 or less. , more preferably 2.30 or less, still more preferably 2.00 or less, and even more preferably 1.90 or less.
  • Tan ⁇ (Tg) represents the ease of deformation when a local temperature rise occurs. The higher the tan ⁇ (Tg), the easier it is to deform when pressure is applied, and the easier it is for toner to enter gaps. . When the tan ⁇ (Tg) is equal to or higher than the above lower limit, the fixability tends to be good.
  • tan ⁇ (Tg) When the tan ⁇ (Tg) is equal to or less than the above upper limit, blocking during storage of the toner is suppressed, and the storage stability tends to be improved, and the occurrence of toner blowout during endurance under high temperature and high humidity is likely to be suppressed. Further, when tan ⁇ (Tg) is within the above range, the area of the trapezoid tends to be within the above range.
  • the first toner of the present disclosure has a tan ⁇ (100° C.) of preferably 0.75 or more, more preferably 0.80 or more, still more preferably 0.82 or more, while preferably 1.00 Below, more preferably 0.97 or less, still more preferably 0.95 or less.
  • tan ⁇ (100° C.) is equal to or higher than the above lower limit, fixability tends to be good.
  • the tan ⁇ (100° C.) is equal to or less than the above upper limit, deterioration of the storage stability of the toner is likely to be suppressed, and the occurrence of toner ejection is likely to be suppressed.
  • the area of the trapezoid is likely to be within the above range.
  • the first toner of the present disclosure has a bulk density (CBD) after conditioning determined using a powder fluidity analyzer of 0.527 g/mL or more and 0.550 g/mL or less.
  • CBD bulk density
  • a powder fluidity analyzer for example, a powder rheometer FT4 (trade name, manufactured by Freeman Technology) can be used.
  • Conditioning in the present disclosure corresponds to the operation of filling toner. Therefore, the bulk density after conditioning simulates the bulk density of densely packed toner in a toner pool formed during toner development.
  • the CBD of the toner it is possible to refer to publicly known documents related to powder fluidity analyzers. Business Division, September 1, 2007 first edition) and other known documents (especially pages 6 to 7 and 10) can be referred to.
  • the CBD in the present disclosure is not necessarily limited only to the contents described in the above-mentioned known documents.
  • a conditioning container having an inner diameter of 50 mm and a total height of 140 mm is filled with 100 g of toner, and the toner is allowed to stand for 10 minutes to form a toner layer.
  • the tip speed of the blade provided in the analyzer was set to 60 mm/sec, and the angle of approach of the blade was set to 5° clockwise, and the blade was passed from the surface of the toner layer into the toner layer while stirring the toner layer. , the blade reaches a position 10 mm from the bottom of the conditioning container.
  • the approach angle of the blade means the angle at which the spiral path drawn by the blade intersects the surface of the toner layer.
  • the approach angle of the blade was changed to be 2° clockwise, and while stirring the toner layer, the blade was moved to a position 1 mm from the bottom of the conditioning container. lower.
  • the approach angle of the blade was changed to 5° counterclockwise, and while stirring the toner layer, the blade was moved to a position 100 mm from the bottom of the conditioning container. to raise (Fifth step) The blade is pulled up from the toner layer surface.
  • excess toner adhering to the blade pulled up from the surface of the toner layer in the fifth step is brushed off.
  • the conditioning container it is preferable to use a conditioning container in which an accessory container having only a side surface is stacked on top of a measurement container having a bottom surface and side surfaces and connected thereto.
  • a conditioning container for example, a cylindrical measurement container having a clamped bottom surface and a cylindrical accessory container having only a side surface are stacked on top of the measurement container and connected by a splitter.
  • the first toner of the present disclosure has a flowability of 80% or greater. As a result, the first toner of the present disclosure is less likely to form toner pools, and deterioration of print quality is suppressed.
  • the fluidity of toner is measured by the following method. Three types of sieves having mesh openings of 150 ⁇ m, 75 ⁇ m, and 45 ⁇ m are stacked in this order, and 4 g of toner is accurately weighed and placed on the top sieve.
  • Fluidity (%) 100 - (a + b + c)
  • the BET specific surface area of the first toner of the present disclosure is not particularly limited, but is preferably 1.00 m 2 /g or more, more preferably 1.50 m 2 /g or more, and still more preferably 1.70 m 2 /g or more. On the other hand, it is preferably 2.00 m 2 /g or less, more preferably 1.90 m 2 /g or less.
  • the BET specific surface area of the toner can be used as an indicator of the mode of attachment of the external additive. When the BET specific surface area of the toner is within the above range, the external additive is appropriately adhered to the colored resin particles, so that the balance between low-temperature fixability and storage stability and fluidity tend to be good.
  • the BET specific surface area of the toner is less than the above lower limit, the amount of the external additive is too small or the external additive is too embedded inside the colored resin particles, resulting in deterioration of blocking resistance and fluidity. There is a possibility that it will decrease, and there is a tendency that toner ejection will easily occur.
  • the BET specific surface area of the toner exceeds the above upper limit, the adhesion amount of the external additive is too large, and the low-temperature fixability may deteriorate.
  • a known method can be used to measure the BET specific surface area of the toner.
  • Examples of the measurement of the BET specific surface area of the toner include a method of measuring by a nitrogen adsorption method (BET method) using a BET specific surface area measuring device (trade name: Macsorb HM model-1208, manufactured by Mountec). .
  • the first toner of the present disclosure having the above-described properties is characterized by, for example, the composition, molecular weight and content of the binder resin contained in the toner, the type and content of the external additive, and the external additive treatment conditions. It can be obtained by adjusting the production conditions.
  • the viscoelasticity of the toner can be controlled mainly by the composition, molecular weight and content of the binder resin and the type and content of the external additive.
  • the CBD and fluidity of the toner can be controlled mainly by adjusting the type and amount of the external additive and the external additive treatment conditions.
  • the looser the external addition treatment conditions such as the slower peripheral speed of the stirring blade during the external addition treatment or the shorter time for the external addition treatment, the smaller the CBD of the toner and the lower the flowability tends to be.
  • the CBD of the toner tends to increase and the fluidity tends to increase as the external addition treatment conditions become more severe, such as the peripheral speed of the stirring blade during the external addition treatment is higher or the external addition treatment time is longer.
  • CBD tends to increase and fluidity tends to be higher when the external addition treatment is performed in two stages rather than in one stage.
  • each component used in the production of the toner adopts the preferred form described later, and the external addition treatment conditions are set to the preferred conditions described later. It is effective to make it a condition.
  • Method for producing colored resin particles In general, methods for producing colored resin particles are broadly classified into dry methods such as pulverization methods and wet methods such as emulsion polymerization aggregation methods, suspension polymerization methods, and dissolution suspension methods.
  • a wet method is preferable because it is easy to obtain a toner having excellent printing properties such as flexibility.
  • polymerization methods such as emulsion polymerization aggregation method and suspension polymerization method are preferable because it is easy to obtain a toner having a relatively small particle size distribution on the order of microns. preferable.
  • emulsified polymerizable monomers are polymerized to obtain a fine resin particle emulsion, which is aggregated with a colorant dispersion or the like to produce colored resin particles.
  • dissolution suspension method a solution in which toner components such as a binder resin and a colorant are dissolved or dispersed in an organic solvent is formed into droplets in an aqueous medium, and the organic solvent is removed to produce colored resin particles.
  • a known method can be used.
  • the colored resin particles used in the first toner of the present disclosure can be produced by adopting a wet method or a dry method, but the wet method is preferable, and among the wet methods, the suspension polymerization method is particularly preferable. and can be manufactured by the following process.
  • A Suspension polymerization method
  • A-1 Preparation step of polymerizable monomer composition
  • Other additives are mixed to prepare a polymerizable monomer composition.
  • Mixing in preparing the polymerizable monomer composition is performed using, for example, a media-type dispersing machine.
  • a polymerizable monomer refers to a monomer having a polymerizable functional group, and the polymerizable monomer polymerizes to form a binder resin. It is preferred to use a monovinyl monomer as the main component of the polymerizable monomer.
  • monovinyl monomers examples include styrene; styrene derivatives such as vinyl toluene and ⁇ -methylstyrene; acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid 2 - acrylic acid esters such as ethylhexyl and dimethylaminoethyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate; acrylonitrile , and nitrile compounds such as methacrylonitrile; amide compounds such as acrylamide and methacrylamide; olefins such as ethylene, propylene, and butylene; These monovinyl monomers may be used alone or in combination
  • the polymerizable monomer is at least one monovinyl monomer selected from the group consisting of styrene, styrene derivatives, acrylic acid esters, and methacrylic acid esters, because it is easy to obtain a toner having the specific viscoelasticity.
  • acrylate ester at least one selected from the group consisting of n-butyl acrylate, propyl acrylate and 2-ethylhexyl acrylate is preferred, and as the methacrylate ester, n-butyl methacrylate is preferred. , propyl methacrylate and 2-ethylhexyl methacrylate are preferred.
  • the content of styrene in the total 100 parts by mass of the monovinyl monomer is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, from the viewpoint that a toner having the specific viscoelasticity can be easily obtained. , preferably 90 parts by mass or less, more preferably 80 parts by mass or less.
  • the monovinyl monomer contains styrene and at least one selected from the group consisting of acrylic acid esters and methacrylic acid esters, and styrene and ,
  • the mass ratio (styrene: (meth)acrylic acid ester) to the total of acrylic acid ester and methacrylic acid ester is preferably in the range of 50:50 to 90:10, 60:40 to 80:20 It is more preferable to be within the range.
  • the content of the monovinyl monomer is appropriately adjusted so as to have the specific viscoelasticity.
  • the total amount of the monovinyl monomers is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, based on 100 parts by mass of the polymerizable monomers.
  • the polymerizable monomer preferably contains an arbitrary crosslinkable polymerizable monomer together with the monovinyl monomer.
  • a crosslinkable polymerizable monomer By containing a crosslinkable polymerizable monomer, a toner having the specific viscoelasticity described above can be easily obtained, and hot offset resistance and storage stability can be improved.
  • a crosslinkable polymerizable monomer refers to a monomer having two or more polymerizable functional groups.
  • crosslinkable polymerizable monomers examples include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; alcohols having two or more hydroxyl groups such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate; ester compounds in which two or more carboxylic acids are ester-bonded; other divinyl compounds such as N,N-divinylaniline and divinyl ether; compounds having three or more vinyl groups; These crosslinkable polymerizable monomers may be used alone or in combination of two or more.
  • aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof
  • alcohols having two or more hydroxyl groups such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate
  • ester compounds in which two or more carboxylic acids are ester-bonded
  • other divinyl compounds such as N,N-divinylaniline and divinyl ether
  • the content of the crosslinkable polymerizable monomer is appropriately adjusted so that the toner has the specific viscoelasticity, and is not particularly limited, but is usually 0.1 per 100 parts by mass of the monovinyl monomer. 5.0 parts by mass, preferably 0.3 to 2.0 parts by mass, more preferably 0.5 to 1.0 parts by mass.
  • the polymerizable monomer preferably contains a macromonomer together with the monovinyl monomer.
  • macromonomers include, for example, reactive oligomers and polymers having a polymerizable carbon-carbon unsaturated double bond at the end of the molecular chain and having a number average molecular weight of usually 1,000 to 30,000. can be mentioned.
  • the macromonomer include styrene macromonomer, styrene-acrylonitrile macromonomer, polyacrylate macromonomer and polymethacrylate macromonomer.
  • At least one selected from polyacrylic acid ester macromonomers and polymethacrylic acid ester macromonomers is preferably used because the glass transition temperature (Tg) in the temperature-tan ⁇ curve can be easily set within the above specific range.
  • the acrylic acid ester used in the polyacrylate macromonomer include those similar to the acrylic acid esters that can be used as the monovinyl monomer, and methacrylic acid used in the polymethacrylic acid ester macromonomer.
  • esters include the same methacrylic acid esters that can be used as the monovinyl monomer.
  • the macromonomer among others, it is preferable to appropriately select and use a macromonomer in which the glass transition temperature (Tg) of the resulting binder resin becomes higher when it is contained in the polymerizable monomer than when it is not contained. , the glass transition temperature (Tg) in the temperature-tan ⁇ curve is easily within the preferred range.
  • a commercially available product may be used as the macromonomer. Examples of commercially available macromonomers include macromonomer series AA-6, AS-6, AN-6S, AB-6 and AW-6S manufactured by Toagosei Co., Ltd. The macromonomers may be used singly or in combination of two or more.
  • the content of the macromonomer is appropriately adjusted so that the toner has the specific viscoelasticity. It is preferably 0.03 to 5 parts by mass, more preferably 0.05 to 1 part by mass.
  • the content of the polymerizable monomer is appropriately adjusted so that the toner has the specific viscoelasticity, and is not particularly limited. On the contrary, it is preferably 60 to 95 parts by mass, more preferably 65 to 90 parts by mass, still more preferably 70 to 85 parts by mass.
  • the solid content refers to all components other than the solvent, and liquid monomers and the like are also included in the solid content.
  • a colorant used in conventional toners can be appropriately selected and used, and is not particularly limited.
  • black, cyan, yellow, and magenta colorants can be used.
  • black colorants that can be used include carbon black, titanium black, and magnetic powders such as zinc iron oxide and nickel iron oxide.
  • the cyan colorant include phthalocyanine pigments such as copper phthalocyanine pigments and derivatives thereof, cyan pigments such as anthraquinone pigments, and cyan dyes. Specifically, for example, C.I. I. Pigment Blue 2, 3, 6, 15, 15:1, 15:2, 15:3, 15:4, 16, 17:1, 60; C.I. I.
  • yellow colorants examples include azo pigments such as monoazo pigments and disazo pigments, yellow pigments such as condensed polycyclic pigments, and yellow dyes.
  • azo pigments such as monoazo pigments and disazo pigments
  • yellow pigments such as condensed polycyclic pigments
  • yellow dyes Specifically, for example, C.I. I. Pigment Yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, 213, 214; C.I. I. Solvent Yellow 98, 162 and the like can be mentioned.
  • magenta colorant examples include azo pigments such as monoazo pigments and disazo pigments, magenta pigments such as condensed polycyclic pigments such as quinacridone pigments, and magenta dyes.
  • azo pigments such as monoazo pigments and disazo pigments
  • magenta pigments such as condensed polycyclic pigments such as quinacridone pigments
  • magenta dyes Specifically, for example, C.I. I. Pigment Red 31, 48, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 150, 163, 170, 184, 185, 187, 202, 206, 207, 209, 237, 238, 251, 254, 255, 269; I. Pigment Violet 19; C.I. I.
  • the colorants may be used singly or in combination of two or more.
  • Carbon black is preferable as the black colorant because it is easy to obtain a toner having the desired CBD and fluidity.
  • cyan colorant phthalocyanine pigments such as copper phthalocyanine pigments and derivatives thereof are preferred. I. Pigment Blue 15:3 is particularly preferred.
  • yellow colorant azo pigments such as disazo pigments are preferred, and among them C.I. I. Pigment Yellow 155 is particularly preferred.
  • magenta colorant condensed polycyclic pigments such as quinacridone pigments are preferred, and C.I. I. Pigment Red 122 is particularly preferred.
  • the content of the colorant is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and still more preferably 7 to 13 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers.
  • the content of the colorant is within the above range, a toner having desired CBD and fluidity can be easily obtained.
  • the polymerizable monomer composition contains a softening agent.
  • a softening agent By containing the softening agent, the releasability of the toner from the fixing roll during fixing can be improved. Any softening agent that is generally used as a toner softening agent or releasing agent can be used without particular limitation.
  • ester waxes examples thereof include low molecular weight polyolefin waxes and modified waxes thereof; petroleum waxes such as paraffin; mineral waxes such as ozokerite; synthetic waxes such as Fischer-Tropsch wax; ester waxes such as dipentaerythritol ester and carnauba; Among them, ester waxes are preferred from the viewpoint of adjusting the viscoelasticity of the toner and improving the balance between storage stability and low-temperature fixability of the toner, and more preferred than synthetic ester waxes obtained by esterifying an alcohol and a carboxylic acid. A polyfunctional ester wax obtained by esterifying a monocarboxylic acid with a polyfunctional ester wax is more preferable.
  • polyfunctional ester wax for example, at least one selected from the group consisting of pentaerythritol ester compounds, glycerin ester compounds and dipentaerythritol ester compounds can be preferably used.
  • Preferred polyfunctional ester waxes include, for example, pentaerythritol ester compounds such as pentaerythritol tetrapalmitate, pentaerythritol tetrabehenate, and pentaerythritol tetrastearate; hexaglycerin tetrabehenate tetrapalmitate, hexaglycerin Glycerin ester compounds such as octabehenate, pentaglycerin heptabhenate, tetraglycerin hexabehenate, triglycerin pentabehenate, diglycerin tetrabehenate, glycerin tribehenate; dipentaerythr
  • the weight average molecular weight Mw of the softening agent is not particularly limited, but is preferably in the range of 400-3500, more preferably in the range of 500-3000.
  • the weight average molecular weight Mw of the softening agent can be measured by the same method as for the weight average molecular weight Mw of the polymer described below.
  • the molecular weight can also be calculated from the structural formula by extracting with a solvent, decomposing into alcohol and carboxylic acid by hydrolysis, and analyzing the composition.
  • the weight average molecular weight Mw of the ester wax is the same as the molecular weight calculated from the structural formula.
  • the melting point of the softening agent is preferably in the range of 50 to 90° C., preferably 60 to 85° C. °C, and even more preferably 70 to 80°C.
  • the softening agent is preferably It is used in a proportion of 1 to 30 parts by mass, more preferably 5 to 20 parts by mass.
  • the said softening agent can be used individually by 1 type or in combination of 2 or more types.
  • the polymerizable monomer composition contains a positively or negatively charged charge control agent. Thereby, the chargeability of the toner can be improved.
  • the charge control agent is not particularly limited as long as it is generally used as a charge control agent for toner.
  • a positively or negatively chargeable charge control resin is preferable because it can impart (charging stability) to the toner particles.
  • a functional group-containing copolymer can be used as the positively or negatively chargeable charge control resin.
  • the positive charge control resin for example, a functional group-containing copolymer containing a structural unit containing a functional group such as an amino group, a quaternary ammonium group, or a quaternary ammonium salt-containing group can be used.
  • polyamine resins, quaternary ammonium group-containing copolymers and quaternary ammonium base-containing copolymers can be used as an amino group, a quaternary ammonium group, or a quaternary ammonium salt-containing group.
  • a functional group-containing copolymer containing a structural unit containing a functional group such as a sulfonic acid group, a sulfonate-containing group, a carboxylic acid group, or a carboxylate-containing group is used.
  • Examples include sulfonic acid group-containing copolymers, sulfonic acid group-containing copolymers, carboxylic acid group-containing copolymers, and carboxylic acid group-containing copolymers.
  • These charge control resins may be used alone or in combination of two or more.
  • the above-mentioned functional group-containing copolymer used as a positively or negatively chargeable charge control resin, among others, has the above functional group-containing copolymer because it is easy to obtain a toner having the specific viscoelasticity.
  • the proportion of group-containing structural units is preferably 10% by mass or less, more preferably 8% by mass or less.
  • the ratio of the functional group-containing structural unit in the functional group-containing copolymer is 1.1. It is preferably 0% by mass or more, more preferably 3.0% by mass or more.
  • the charge control resin contains sufficient functional groups, the charge control resin is easily localized in the vicinity of the surface of the colored resin particles, and the charge control resin functions like a shell of the colored resin particles. It is presumed that the storage stability is improved and the occurrence of blowout during durability under high temperature and high humidity is suppressed.
  • the proportion of functional group-containing structural units in the functional group-containing copolymer may be simply referred to as "functional group amount”.
  • the above functional group-containing copolymer used as a positively or negatively chargeable charge control resin has high compatibility with the above polymerizable monomer, making it easy to obtain a toner having the specific viscoelasticity.
  • the styrene-acrylic resin is preferable.
  • the styrene-acrylic copolymer may be a copolymer of a vinyl aromatic hydrocarbon monomer and a (meth)acrylate monomer.
  • the functional group-containing copolymer used as a positively or negatively chargeable charge control resin preferably has a glass transition temperature (Tg) of 50 to 110°C, more preferably 60 to 100°C. is more preferred.
  • Tg glass transition temperature
  • the functional group-containing copolymer is easily localized in the vicinity of the surface of the colored resin particles and can function like a shell. It is presumed that the storage stability of the toner is improved when the is sufficiently high.
  • the glass transition temperature (Tg) of the functional group-containing copolymer is measured by the same method as the glass transition temperature (Tg) of the toner described above.
  • the functional group-containing copolymer used as a positively or negatively chargeable charge control resin preferably has a weight average molecular weight Mw of 5,000 to 30,000, more preferably 10,000 to 25,000.
  • charge control agents other than positive charge control resins include nigrosine dyes, quaternary ammonium salts, triaminotriphenylmethane compounds, and imidazole compounds.
  • charge control agents other than negative charge control resins include azo dyes containing metals such as Cr, Co, Al, and Fe, metal salicylates, and metal alkylsalicylate compounds. The charge control agent can be used alone or in combination of two or more.
  • the charge control agent is usually 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, more preferably 0.6 to 1.5 parts by weight, per 100 parts by weight of the monovinyl monomer. It is used in proportions of parts by mass.
  • the content of the charge control agent is equal to or higher than the above lower limit, the occurrence of fogging can be suppressed. can be done.
  • the CBD of the toner tends to increase and the fluidity tends to increase.
  • the content of the charge control agent is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • the polymerizable monomer composition further contains a molecular weight modifier.
  • the molecular weight modifier is not particularly limited as long as it is generally used as a molecular weight modifier for toners. Examples include t-dodecylmercaptan, n-dodecylmercaptan, n-octylmercaptan, Mercaptans such as 4,6,6-pentamethylheptane-4-thiol; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N,N'-dimethyl-N,N'-diphenylthiuram disulfide, N, Thiuram disulfides such as N'-dioctadecyl-N,N'-diisopropylthiuram disulfide; These molecular weight modifiers may be used alone or in combination of two or
  • the content of the molecular weight modifier is adjusted so that the weight-average molecular weight Mw of the polymer contained in the binder resin falls within the preferred range described later. It is preferable to The molecular weight modifier is preferably used in a proportion of 1.0 to 3.0 parts by weight, more preferably 1.1 to 2.0 parts by weight, per 100 parts by weight of the monovinyl monomer. As the content of the molecular weight modifier increases, the weight average molecular weight of the polymer contained in the binder resin tends to decrease.
  • the molecular weight modifier tends to exist on the surface of the colored resin particles, and the higher the content of the molecular weight modifier, the smaller the CBD of the toner and the lower the fluidity.
  • the content of the molecular weight modifier is within the above range, a toner having desired CBD and fluidity can be easily obtained.
  • A-2 Suspension step of obtaining suspension (droplet formation step)
  • the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer, a polymerization initiator is added, and droplets of the polymerizable monomer composition are formed.
  • the polymerization initiator may be added after the polymerizable monomer composition is dispersed in the aqueous medium and before droplet formation. It may be added to the monomer composition.
  • the method of forming droplets is not particularly limited, but examples include (in-line type) emulsifying and dispersing machine (manufactured by Taihei Kiko Co., Ltd., trade name: Milder), high-speed emulsifying and dispersing machine (manufactured by Primix, trade name: TK Homo Mixer). It is carried out using an apparatus capable of strong stirring such as MARK II type).
  • Polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate; 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-methyl-N-(2- hydroxyethyl)propionamide), 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(2,4-dimethylvaleronitrile), and 2,2′-azobisisobutyronitrile azo compounds such as di-t-butyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylbutanoate, t-hexylperoxy-2 -ethylbutanoate, diisopropylperoxydicarbonate, di-t-butylperoxyisophthalate, and t-butylperoxyisobutyrate.
  • organic peroxide because it can reduce the residual polymerizable monomer and is excellent in printing durability.
  • peroxides peroxyesters are preferred because they have good initiator efficiency and can reduce residual polymerizable monomers. is more preferred.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used in the polymerization reaction of the polymerizable monomer composition is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monovinyl monomer. 3 to 15 parts by mass, particularly preferably 1 to 10 parts by mass.
  • an aqueous medium refers to a medium containing water as a main component.
  • the aqueous medium preferably contains a dispersion stabilizer.
  • Dispersion stabilizers include, for example, sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; metals such as aluminum oxide and titanium oxide oxides; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; inorganic compounds such as; water-soluble polymers such as polyvinyl alcohol, methylcellulose, and gelatin; anionic surfactants; Organic compounds such as nonionic surfactants; amphoteric surfactants; These dispersion stabilizers can be used singly or in combination of two or more.
  • inorganic compounds are preferable, and colloids of poorly water-soluble metal hydroxides are particularly preferable as the aqueous medium containing the dispersion stabilizer.
  • an inorganic compound especially a colloid of a poorly water-soluble metal hydroxide, the particle size distribution of the colored resin particles can be narrowed, and the amount of the dispersion stabilizer remaining after washing can be reduced.
  • the polymerized toner can reproduce sharp images and does not deteriorate environmental stability.
  • the colloid of poorly water-soluble metal hydroxide is, for example, at least one selected from alkali metal hydroxides and alkaline earth metal hydroxides, and water-soluble polyvalent metal salts (alkaline earth metal hydroxides).
  • Alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • Alkaline earth metal hydroxides include barium hydroxide and calcium hydroxide.
  • the water-soluble polyvalent metal salt may be any water-soluble polyvalent metal salt other than the compounds corresponding to the alkaline earth metal hydroxides. Examples include magnesium chloride, magnesium phosphate, magnesium sulfate, and the like.
  • magnesium metal salts such as calcium chloride, calcium nitrate, calcium acetate and calcium sulfate; aluminum metal salts such as aluminum chloride and aluminum sulfate; barium salts such as barium chloride, barium nitrate and barium acetate; zinc chloride and zinc nitrate , zinc salts such as zinc acetate; Among these, magnesium metal salt, calcium metal salt, and aluminum metal salt are preferred, magnesium metal salt is more preferred, and magnesium chloride is particularly preferred.
  • the water-soluble polyvalent metal salts can be used either singly or in combination of two or more.
  • the method of reacting at least one selected from the alkali metal hydroxides and alkaline earth metal hydroxides described above with the water-soluble polyvalent metal salt described above in an aqueous medium is not particularly limited.
  • a method of mixing at least one aqueous solution selected from alkali metal salts and alkaline earth metal hydroxides with an aqueous solution of a water-soluble polyvalent metal salt can be used.
  • the content of the dispersion stabilizer is appropriately adjusted so as to obtain a toner having a desired particle size, and is not particularly limited. It is preferably 0.5 to 10 parts by mass, more preferably 1.0 to 8.0 parts by mass.
  • the content of the dispersion stabilizer is equal to or higher than the above lower limit, the droplets of the polymerizable monomer composition can be sufficiently dispersed so as not to coalesce in the suspension.
  • the content of the dispersion stabilizer is equal to or less than the above upper limit, it is possible to prevent the viscosity of the suspension from increasing during granulation, and to avoid the problem of the suspension clogging the granulator. can.
  • the content of the dispersion stabilizer is usually 1-15 parts by mass, preferably 1-8 parts by mass, per 100 parts by mass of the aqueous medium.
  • (A-3) Polymerization step After forming droplets of the polymerizable monomer composition as in (A-2) above, in the presence of a polymerization initiator, the polymerizable monomer composition is subjected to a polymerization reaction to form colored resin particles. That is, an aqueous dispersion in which droplets of the polymerizable monomer composition are dispersed is heated to initiate polymerization and form an aqueous dispersion of colored resin particles.
  • the heating conditions are preferably adjusted so that the weight-average molecular weight Mw of the polymer of the polymerizable monomer falls within the preferable range described later, and the heating temperature is not particularly limited, but is 50° C. or higher. is preferred, and more preferably 60 to 95°C.
  • the heating time is preferably 1 to 20 hours, more preferably 2 to 15 hours.
  • an external additive can be added to the colored resin particles obtained by the polymerization step to obtain the first toner of the present disclosure.
  • (or also referred to as "capsule type) as a core layer of colored resin particles.
  • Core-shell type colored resin particles have a structure in which the outside of a core layer is covered with a shell layer formed of a material different from that of the core layer.
  • the method for producing core-shell type colored resin particles using the colored resin particles obtained by the above polymerization step is not particularly limited, and can be produced by a conventionally known method.
  • An in situ polymerization method and a phase separation method are preferable from the viewpoint of production efficiency.
  • a method for producing core-shell type colored resin particles by an in situ polymerization method will be described below.
  • a polymerizable monomer for forming a shell layer (polymerizable monomer for shell) and a polymerization initiator are added to the aqueous medium in which the colored resin particles obtained by the above polymerization step are dispersed, and polymerized.
  • core-shell type colored resin particles can be obtained.
  • the same polymerizable monomer as described above can be used.
  • monomers such as styrene, acrylonitrile, and methyl methacrylate, which give polymers having Tg exceeding 80°C, singly or in combination of two or more.
  • Polymerization initiators used for polymerization of the polymerizable monomer for the shell include metal persulfates such as potassium persulfate and ammonium persulfate; 2,2′-azobis(2-methyl-N-(2-hydroxyethyl)propion azo initiators such as amide) and 2,2′-azobis-(2-methyl-N-(1,1-bis(hydroxymethyl)2-hydroxyethyl)propionamide); water-soluble polymerization initiators such as can be mentioned. These can be used alone or in combination of two or more.
  • the amount of the polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymerizable monomer for shell.
  • the polymerization temperature of the shell layer is preferably 50°C or higher, more preferably 60 to 95°C.
  • the polymerization reaction time is preferably 1 hour to 20 hours, more preferably 2 hours to 15 hours.
  • an inorganic compound when used as the dispersion stabilizer, it is preferable to dissolve and remove the dispersion stabilizer in water by adding an acid or alkali to the aqueous dispersion of the colored resin particles.
  • an acid when a sparingly water-soluble inorganic hydroxide colloid is used as the dispersion stabilizer, it is preferable to add an acid to adjust the pH of the aqueous dispersion of colored resin particles to 6.5 or less.
  • the acid to be added inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as formic acid and acetic acid can be used. preferred.
  • dehydration and filtration Various known methods can be used for dehydration and filtration, and there is no particular limitation. Examples thereof include centrifugal filtration, vacuum filtration, and pressure filtration. Moreover, after dehydration, drying may be performed as necessary. The drying method is not particularly limited, and various methods can be used.
  • (B) Pulverization Method When producing colored resin particles by employing a pulverization method, for example, the process is carried out as follows. First, a binder resin, a coloring agent, a softening agent, a charge control agent, and optionally other additives are mixed in a mixer such as a ball mill, a V-type mixer, or an FM mixer (trade name: Nippon Coke (manufactured by Kogyo Co., Ltd.), a high-speed dissolver, an internal mixer, a Fallberg, or the like. Next, the mixture obtained above is kneaded while being heated using a pressure kneader, a twin-screw extruder kneader, rollers, or the like.
  • a mixer such as a ball mill, a V-type mixer, or an FM mixer (trade name: Nippon Coke (manufactured by Kogyo Co., Ltd.), a high-speed dissolver, an internal mixer, a Fallberg, or
  • the resulting kneaded product is coarsely pulverized using a pulverizer such as a hammer mill, cutter mill, or roller mill. Furthermore, after fine pulverization using a pulverizer such as a jet mill or a high-speed rotary pulverizer, the colored resin particles are classified to a desired particle size by a classifier such as an air classifier or an air classifier, and then pulverized.
  • a classifier such as an air classifier or an air classifier
  • the binder resin, colorant, softening agent, and charge control agent used in the pulverization method can be those listed in (A) the suspension polymerization method described above.
  • the colored resin particles obtained by the pulverization method are used in a method such as an in situ polymerization method in the same manner as the colored resin particles obtained by the above-mentioned (A) suspension polymerization method to produce core-shell type colored resin particles.
  • binder resin other resins that have been widely used in toner can also be used.
  • specific examples of the binder resin used in the pulverization method include polystyrene, styrene-butyl acrylate copolymer, polyester resin, and epoxy resin.
  • Colored Resin Particles Colored resin particles are obtained by the production method such as (A) the suspension polymerization method or (B) the pulverization method described above.
  • the colored resin particles contained in the first toner of the present disclosure are described below.
  • the colored resin particles described below include both core-shell type and non-core-shell type.
  • the colored resin particles used in the first disclosure contain a binder resin, a colorant, a softening agent and a charge control agent, and may further contain other additives as necessary.
  • binder resin contained in the colored resin particles examples include polymers obtained by polymerizing the polymerizable monomers mentioned in the above-mentioned (A) suspension polymerization method.
  • the polymer may be either a homopolymer or a copolymer.
  • Preferred polymerizable monomers from which each structural unit of the polymer is derived are the same as the preferred polymerizable monomers described in the above (A) suspension polymerization method.
  • the binder resin contained in the colored resin particles is styrene, an acrylic acid ester, and a methacrylic acid. It is preferable to contain a polymer of one or two or more polymerizable monomers containing at least one monovinyl monomer selected from the group consisting of esters, and from styrene, acrylic acid esters and methacrylic acid esters.
  • a polymer of one or more polymerizable monomers including at least one selected from the group consisting of:
  • the structure and ratio of each structural unit in all the structural units of the polymer can be obtained from the charged amount when synthesizing the polymer, and can be calculated from the integral value by 1 H-NMR measurement. can be done.
  • the weight-average molecular weight Mw of the polymer contained in the binder resin is preferably 4.40 from the viewpoint that the toner having the specific viscoelasticity described above can be easily obtained and the low-temperature fixability and storage stability of the toner can be improved in a well-balanced manner. ⁇ 10 5 or more and 7.00 ⁇ 10 5 or less. Among them, the lower limit of the weight average molecular weight Mw is more preferably 4.50 ⁇ 10 5 or more, still more preferably 4.60 ⁇ 10 5 or more, from the viewpoint of improving the storage stability of the toner.
  • the upper limit of the molecular weight Mw is more preferably 6.50 ⁇ 10 5 or less, still more preferably 6.00 ⁇ 10 5 or less, from the viewpoint of improving the low-temperature fixability of the toner.
  • the polymer contained in the binder resin is typically a polymer of the polymerizable monomers. The smaller the weight average molecular weight Mw of the polymer, the lower the glass transition temperature (Tg) of the toner specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz, and the larger the area of the trapezoid. When the weight-average molecular weight Mw of the polymer is within the above range, the toner having the specific viscoelasticity is easily obtained.
  • the weight average molecular weight Mw of the polymer can be obtained by polystyrene conversion by GPC.
  • a polymer to be measured dissolved in tetrahydrofuran (THF) is usually used.
  • a toner dissolved in tetrahydrofuran (THF) is used as a measurement sample, and the measurement results indicate that the polymer contained as the binder resin is
  • the weight-average molecular weight Mw of the polymer contained as the binder resin can be determined using the data obtained by subtracting the pre-measured peaks for the polymers other than the charge control resin, the softening agent, and the like.
  • the binder resin contained in the colored resin particles is typically a polymer of the polymerizable monomer.
  • a small amount of used polyester-based resin, epoxy-based resin, or unreacted polymerizable monomer may be included.
  • the content of the polyester resin contained in 100 parts by mass of the binder resin is preferably 5 parts by mass or less, more preferably 1 part by mass or less, and is 0.1 part by mass or less. is more preferable, and it is particularly preferable not to contain a polyester-based resin.
  • the content of the polyester-based resin is equal to or less than the above upper limit value, the environmental stability of the toner can be improved, and in particular, changes in charging of the toner due to changes in humidity can be suppressed.
  • the binder resin contains a resin other than the polymer of the polymerizable monomer, the toner having the specific viscoelasticity is easily obtained.
  • the content of the polymonomer polymer is preferably 95 parts by mass or more, more preferably 97 parts by mass or more, and even more preferably 99 parts by mass or more.
  • the total content of the binder resin is preferably 70 to 99 parts by mass, based on 100 parts by mass of the total solid content of the colored resin particles, from the viewpoint that the toner having the specific viscoelasticity is easily obtained. It is preferably 75 to 97 parts by mass, more preferably 80 to 95 parts by mass.
  • the colorant, softening agent, and charge control agent contained in the colored resin particles are the same as those mentioned in (A) the suspension polymerization method.
  • the content of the colorant contained in the colored resin particles is appropriately adjusted according to the type of the colorant so that the desired color development is obtained and the toner has the specific viscoelasticity, and is not particularly limited. is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, still more preferably 7 to 13 parts by mass, based on 100 parts by mass of the binder resin.
  • the content of the softening agent contained in the colored resin particles is preferably from 1 to 30 parts by mass, more than It is preferably 5 to 20 parts by mass.
  • the content of the charge control agent contained in the colored resin particles is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, still more preferably 100 parts by mass of the binder resin. It is 0.6 to 1.5 parts by mass.
  • the content of the charge control agent is equal to or higher than the lower limit, it is possible to suppress the occurrence of fogging. Further, when the content of the charge control agent is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • the volume average particle size (Dv) of the colored resin particles is preferably 3 to 15 ⁇ m, more preferably 4 to 12 ⁇ m.
  • the Dv of the colored resin particles is at least the above lower limit, the fluidity of the toner can be improved, the deterioration of the transferability and the reduction of the image density can be suppressed, and the occurrence of toner blowout during endurance under high temperature and high humidity conditions. can be suppressed.
  • the Dv of the colored resin particles is equal to or less than the above upper limit, it is possible to suppress deterioration in image resolution. Further, when the Dv of the colored resin particles is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • the colored resin particles preferably have a ratio (Dv/Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.0 to 1.3, more preferably 1. 0 to 1.2.
  • Dv/Dn of the colored resin particles is 1.3 or less, deterioration in transferability, image density and resolution can be suppressed.
  • the Dv/Dn of the colored resin particles is 1.3 or less, a toner having desired CBD and fluidity can be easily obtained.
  • the volume-average particle diameter and number-average particle diameter of the colored resin particles can be measured, for example, using a particle size analyzer (manufactured by Beckman Coulter, trade name: Multisizer).
  • the average circularity of the colored resin particles is preferably 0.96 to 1.00, more preferably 0.97 to 1.00, and more preferably 0.98 to 1.00. is more preferable.
  • the average circularity of the colored resin particles is 0.96 or more, fine line reproducibility of printing can be improved.
  • the average circularity of the colored resin particles is 0.96 or more, it is easy to obtain a toner having desired CBD and fluidity.
  • the average circularity of the colored resin particles of the present disclosure is 1 or less, and the average circularity is 1 when the measurement sample is perfectly spherical.
  • circularity is a value obtained by dividing the perimeter of a circle having the same projected area as the particle image by the perimeter of the projected image of the particle.
  • the average circularity serves as an index indicating the degree of unevenness of the surface of the measurement sample, and can be used as a simple method for quantitatively expressing the particle shape.
  • the circularity of the colored resin particles is measured, for example, by using an aqueous solution in which the colored resin particles are dispersed as a sample liquid and using a flow-type particle image analyzer (for example, Simex Co., Ltd., trade name: FPIA-2100, etc.) in the sample liquid.
  • the average circularity is the average circularity of each colored resin particle contained in the sample liquid.
  • the first toner of the present disclosure contains the colored resin particles and an external additive.
  • the external additive By performing external addition treatment by mixing and stirring the colored resin particles with an external additive, the external additive can be adhered to the surface of the colored resin particles to form a one-component toner (developer).
  • the one-component toner may be further mixed and stirred with carrier particles to form a two-component developer.
  • the inorganic fine particles A having a number average primary particle size of 36 to 100 nm are preferably contained as an external additive. If the number-average primary particle diameter of the inorganic fine particles A is less than 36 nm, the CBD value may become too large, and the spacer effect may decrease, which may adversely affect printing performance such as fogging. . On the other hand, when the number average primary particle diameter of the inorganic fine particles A exceeds 100 nm, the CBD value may become too small, or the fluidity may decrease. is likely to be liberated, and the function as an external additive may deteriorate, adversely affecting printing performance.
  • the number average primary particle diameter of the inorganic fine particles A is more preferably 40 nm or more, still more preferably 45 nm as a lower limit, and more preferably 80 nm or less, still more preferably 70 nm or less as an upper limit. Further, the inorganic fine particles A are preferably subjected to a hydrophobic treatment.
  • silane coupling agents, silicone oils, fatty acids, fatty acid metal salts, and the like can be used as hydrophobizing agents. Among these, silane coupling agents and silicone oils are preferred.
  • the lower limit of the content of the inorganic fine particles A is preferably 0.30 parts by mass or more, more preferably 0.50 parts by mass or more, and still more preferably 1 part by mass with respect to 100 parts by mass of the binder resin in the colored resin particles. 00 parts by mass or more, and the upper limit is preferably 2.50 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.50 parts by mass or less.
  • the content of the inorganic fine particles A is at least the above lower limit, the function as an external additive can be sufficiently exerted, so deterioration of printing performance or storage stability is suppressed.
  • the content of the inorganic fine particles A is equal to or less than the above upper limit, separation of the inorganic fine particles A from the surface of the toner particles is suppressed, thereby suppressing deterioration of printing performance. Further, when the content of the inorganic fine particles A is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • inorganic fine particles B having a number average primary particle size of 15 to 35 nm as an external additive.
  • the number-average primary particle diameter of the inorganic fine particles B is less than 15 nm, the inorganic fine particles B tend to be buried from the surface of the colored resin particles to the inside, so that the CBD value may become too large.
  • the inability to impart sufficient fluidity to the toner particles may adversely affect printing performance.
  • the CBD value may become too small, and the ratio of the inorganic fine particles B to the surface of the toner particles (coverage) is lowered, it may not be possible to impart sufficient fluidity to the toner particles.
  • the lower limit of the number average primary particle diameter of the inorganic fine particles B is more preferably 17 nm or more, more preferably 20 nm or more, and the upper limit is more preferably 30 nm or less, still more preferably 25 nm or less.
  • the inorganic fine particles B are subjected to a hydrophobic treatment.
  • the lower limit of the content of the inorganic fine particles B is preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, and still more preferably 0 parts by mass with respect to 100 parts by mass of the binder resin in the colored resin particles.
  • the upper limit is preferably 2.00 parts by mass or less, more preferably 1.50 parts by mass or less, and even more preferably 1.00 parts by mass or less.
  • the content of the inorganic fine particles B is equal to or less than the above upper limit, the release of the inorganic fine particles B from the surface of the toner particles is suppressed, thereby suppressing the deterioration of the charging characteristics and thus suppressing the occurrence of fogging. be done. Further, when the content of the inorganic fine particles B is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • inorganic fine particles C having a number average primary particle size of 6 to 14 nm as an external additive.
  • the number-average primary particle diameter of the inorganic fine particles C is less than 6 nm, the inorganic fine particles C tend to be buried from the surface of the colored resin particles to the inside, so that the CBD value may become too large.
  • the inability to impart sufficient fluidity to the toner particles may adversely affect printing performance.
  • the CBD value may become too small, and the ratio of the inorganic fine particles C to the surface of the toner particles (coverage) is lowered, it may not be possible to impart sufficient fluidity to the toner particles.
  • the number average primary particle diameter of the inorganic fine particles C has a lower limit of preferably 6.5 nm or more, more preferably 7.0 nm or more, and an upper limit of more preferably 12 nm or less, still more preferably 10 nm or less. .
  • the inorganic fine particles C are preferably subjected to a hydrophobic treatment.
  • the lower limit of the content of the inorganic fine particles C is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, and still more preferably 0 parts by mass with respect to 100 parts by mass of the binder resin in the colored resin particles. .20 parts by mass or more, and the upper limit is preferably 1.50 parts by mass or less, more preferably 1.00 parts by mass or less, still more preferably 0.80 parts by mass or less, and even more preferably 0.60 parts by mass. It is below.
  • the content of the inorganic fine particles C is at least the above upper limit, the function as an external additive can be sufficiently exerted, thereby suppressing deterioration of fluidity and deterioration of storage stability.
  • the content of the inorganic fine particles C is equal to or less than the above upper limit, the separation of the inorganic fine particles C from the surface of the toner particles is suppressed, thereby suppressing the deterioration of the charging characteristics and thus causing fogging. Suppressed. Further, when the content of the inorganic fine particles C is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • the first toner of the present disclosure preferably contains any one of the inorganic fine particles A to C, more preferably any two, and even more preferably all three.
  • the viscoelasticity, CBD and fluidity of the toner can be adjusted by appropriately adjusting the particle size and the amount of addition of the inorganic fine particles A to C.
  • Examples of inorganic fine particles A, B and C include silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, calcium phosphate, and cerium oxide.
  • the inorganic fine particles A to C may be made of different materials, but are preferably made of the same material.
  • Each of the inorganic fine particles A to C preferably contains at least one selected from silica and titanium oxide, and more preferably comprises silica.
  • the inorganic fine particles A various commercially available silica fine particles can be used. number average primary particle diameter: 50 nm); As the inorganic fine particles B, various commercially available silica fine particles can be used. name, number average primary particle size: 16 nm); TG-7120 manufactured by Cabot Corporation (trade name, number average primary particle size: 20 nm). As the inorganic fine particles C, various commercially available silica fine particles can be used.
  • organic fine particles D having a number average primary particle diameter of 1.0 ⁇ m or less as an external additive. This facilitates obtaining a toner having desired CBD and fluidity.
  • organic fine particles D are contained as an external additive, filming on the photoreceptor is less likely to occur, and the toner particles are imparted with stable chargeability over time. It is possible to obtain a toner in which image quality hardly deteriorates, especially in a high-temperature and high-humidity environment (HH environment).
  • the lower limit of the number average primary particle diameter of the organic fine particles D is preferably 0.3 ⁇ m or more, more preferably 0.4 ⁇ m or more, and still more preferably 0.4 ⁇ m or more. It is 5 ⁇ m or more, and the upper limit is more preferably 0.9 ⁇ m or less, and still more preferably 0.8 ⁇ m or less.
  • the lower limit of the content of the organic fine particles D is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and still more preferably 0 parts by mass with respect to 100 parts by mass of the binder resin in the colored resin particles. 0.03 parts by mass or more, more preferably 0.04 parts by mass or more, and the upper limit is preferably 0.19 parts by mass or less, more preferably 0.17 parts by mass or less, and still more preferably 0.15 parts by mass. Below, more preferably 0.13 parts by mass or less.
  • the organic fine particles D when the content of the organic fine particles D is equal to or higher than the above lower limit, the organic fine particles D can sufficiently exhibit the function as an external additive, thereby suppressing a decrease in chargeability in a high-temperature and high-humidity environment and causing fogging. can be suppressed.
  • the content of the organic fine particles D is equal to or less than the above upper limit, it is possible to suppress the deterioration of toner fixability due to an excessive amount of the external additive.
  • the content of the organic fine particles D when the content of the organic fine particles D is equal to or less than the above upper limit, separation of the organic fine particles D from the surfaces of the toner particles is suppressed, thereby suppressing a decrease in fluidity.
  • the content of the organic fine particles D when the content of the organic fine particles D is within the above range, it is easy to obtain a toner having desired CBD and fluidity.
  • fatty acid metal salt particles are preferably used as the organic fine particles D.
  • the fatty acid (R-COOH) that induces the fatty acid moiety (R-COO - ) possessed by the fatty acid metal salt particles may be a monocarboxylic acid containing only one carboxyl group (-COOH), and may be a monocarboxylic acid having a chain structure.
  • a carboxylic acid is preferred, a saturated monocarboxylic acid having a chain structure is more preferred, and a linear saturated monocarboxylic acid is even more preferred.
  • the fatty acid moiety (R-- COO.sup.- ) possessed by the fatty acid metal salt particles is preferably derived from a higher fatty acid having a large number of carbon atoms in the alkyl group (R--).
  • the number of carbon atoms in the alkyl group of the fatty acid moiety is not particularly limited, it is preferably 12-24, more preferably 14-22, even more preferably 16-20.
  • Preferable higher fatty acids used as raw materials for fatty acid metal salt particles include, for example, lauric acid (CH 3 (CH 2 ) 10 COOH), tridecanoic acid (CH 3 (CH 2 ) 11 COOH), myristic acid (CH 3 (CH 2 ) 12 COOH), pentadecanoic acid (CH 3 (CH 2 ) 13 COOH), palmitic acid (CH 3 (CH 2 ) 14 COOH), heptadecanoic acid (CH 3 (CH 2 ) 15 COOH), stearic acid (CH 3 ( CH 2 ) 16 COOH), arachidic acid (CH 3 (CH 2 ) 18 COOH), behenic acid (CH 3 (CH 2 ) 20 COOH), lignoceric acid (CH 3 (CH 2 ) 22 COOH) and the like.
  • lauric acid CH 3 (CH 2 ) 10 COOH
  • tridecanoic acid CH 3 (CH 2 ) 11 COOH
  • myristic acid CH 3 (CH 2 ) 12 COOH
  • stearic acid and behenic acid are preferred, and stearic acid is more preferred.
  • These fatty acids used as raw materials for the fatty acid metal salt particles can be used alone or in combination of two or more kinds, but it is preferable to use them alone from the viewpoint of obtaining uniform properties.
  • the metal contained in the fatty acid metal salt particles may be an alkali metal, an alkaline earth metal, or a metal element of Group 12 of the periodic table, such as Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr. , Ba, Zn and the like.
  • an alkaline earth metal or a metal element of Group 12 of the periodic table is preferred, at least one selected from Mg and Zn is more preferred, and Zn is even more preferred.
  • fatty acid metal salt particles various commercially available products can be used.
  • -100F trade name, magnesium stearate particles, number average primary particle size: 0.72 ⁇ m), and the like.
  • the number average primary particle size of the external additive particles used in the present disclosure can be measured, for example, as follows. First, the particle size of each particle of the external additive is measured using a transmission electron microscope (TEM) or the like. The particle diameters of 200 or more external additive particles are thus measured, and the average value is taken as the number-average primary particle diameter of the particles.
  • TEM transmission electron microscope
  • a known external addition treatment method can be employed, and is not particularly limited, but in the present disclosure, the external additive to be added Part of the agent is mixed and stirred with wet colored resin particles and dried to obtain intermediate particles.
  • a method of performing a second step of external addition treatment is preferred.
  • the external addition treatment is performed in two stages in this manner, the external additive added before drying the colored resin particles becomes relatively easily embedded in the surface of the colored resin particles, and is added after drying the colored resin particles.
  • the added external additive becomes relatively difficult to embed in the surface of the colored resin particles.
  • the irregularities on the surface of the toner particles become moderate, so that a toner having desired CBD and fluidity can be easily obtained.
  • the wet colored resin particles used in the first-stage external addition treatment preferably have a moisture content of 5 to 20%, more preferably 6 to 15%, and even more preferably 7 to 12%.
  • the intermediate particles used in the second-stage external addition treatment preferably have a moisture content of 1% or less, more preferably 0.8% or less, and even more preferably 0.5% or less.
  • the external additive added in the first stage of the external addition treatment preferably contains the inorganic fine particles C, and more preferably consists of the inorganic fine particles C described above.
  • the external additive added in the second-stage external addition treatment preferably contains the organic fine particles D, and more preferably contains the organic fine particles D and the inorganic fine particles A and B. This facilitates obtaining a toner having desired CBD and fluidity.
  • the wet colored resin particles may be mixed and stirred with the external additive and then dried, but the wet colored resin particles and the external additive may be dried while being mixed and stirred. It is preferred, that is, mixing and stirring and drying are preferably carried out at the same time.
  • the drying method in the first-stage external addition treatment is not particularly limited, and for example, drying under reduced pressure, vacuum drying, heat drying, or the like can be employed.
  • the external addition treatment in the second step is not particularly limited, but for example, Henschel Mixer (: trade name, manufactured by Mitsui Mining Co., Ltd.), FM Mixer (: trade name, manufactured by Nippon Coke Industry Co., Ltd.), Super Mixer (: trade name , manufactured by Kawada Seisakusho Co., Ltd.), Q Mixer (: trade name, manufactured by Nippon Coke Industry Co., Ltd.), Mechano Fusion System (: trade name, manufactured by Hosokawa Micron Co., Ltd.), and Mechanomill (: trade name, manufactured by Okada Seiko Co., Ltd.). It can be carried out using a stirrer capable of stirring.
  • the CBD and fluidity of the resulting toner can also be adjusted by changing the conditions of the peripheral speed of the stirring blades, the time of the external addition treatment, and the like during the external addition treatment.
  • the peripheral speed of the stirring blade during the external addition treatment is preferably 35 to 55 m/s, more preferably 40 to 50 m/s, in order to easily obtain a toner having desired CBD and fluidity.
  • the time for the external addition treatment is preferably 6 minutes to 15 minutes, more preferably 6 minutes to 12 minutes.
  • the peripheral speed of the stirring blade and the external addition treatment time in the second stage of the external addition treatment is preferable to set the peripheral speed of the stirring blade and the external addition treatment time in the second stage of the external addition treatment as described above.
  • the conditions for mixing and stirring in the first stage of the external addition treatment are not particularly limited.
  • the stirring time can be from 10 hours to 48 hours.
  • the first toner of the present disclosure is one in which the occurrence of blowout during endurance under high temperature and high humidity is suppressed. After the first toner of the present disclosure was left for 24 hours in a high temperature and high humidity environment, the toner was removed from the developing roller of the cartridge after an endurance test in which 5,000 sheets of paper were continuously printed at a print density of 5% in the same environment. It is preferable that the toner does not spill, and more preferably, the toner only spills from a part of the developing roller or does not spill from the developing roller when the cartridge is further tilted after the endurance test.
  • the toner ejection test during endurance under high temperature and high humidity is performed by filling the toner cartridge of the developing device of a commercially available non-magnetic one-component developing printer with the toner, and the cartridge filled with the toner is After leaving it in a high temperature and high humidity (H/H) environment (temperature: 35°C, humidity: 80% RH) for 24 hours in a sealed state so as not to be affected by humidity, it is performed in the same environment. .
  • H/H high temperature and high humidity
  • the toner ejection test can be performed by the same test as the toner ejection test during endurance under high temperature and high humidity conditions in Examples described later.
  • the first toner of the present disclosure has good storage stability and suppresses a decrease in blocking occurrence temperature (heat resistant temperature).
  • the first toner of the present disclosure has a blocking temperature (heat resistant temperature) of preferably 54° C. or higher, more preferably 55° C. or higher, and even more preferably 56° C. or higher.
  • the blocking occurrence temperature of toner is defined as the maximum temperature at which the mass of aggregated toner becomes 5% by mass or less of the total amount of toner when the toner is stored at a constant temperature for 8 hours.
  • the blocking occurrence temperature of the toner can be measured by the same method as the measurement of the heat resistance temperature of the toner in Examples described later.
  • the first toner of the present disclosure has good low-temperature fixability, and a solid image is printed on paper using a printer with a fixing roll temperature of 150° C., and a density reduction rate when a rubbing test is performed on the solid area. However, it is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less.
  • the density reduction rate is obtained from the following formula as a ratio of the difference in image density before and after the rubbing test (ID (before) - ID (after)) to the image density before the rubbing test (ID (before)).
  • Density decrease rate (%) [[ID (before) - ID (after)]/ID (before)] x 100
  • the rubbing test is carried out by attaching the measurement part to a fastness tester with an adhesive tape, placing a load of 500 g, and rubbing the part back and forth five times with a rubbing terminal wrapped with a cotton cloth.
  • a solid area is an area in which developer is controlled to adhere to all of the dots (virtual dots controlled by the printer control unit) within the area.
  • the second toner of the present disclosure is a toner containing colored resin particles containing a binder resin, a coloring agent, a softening agent and a charge control agent, and an external additive, containing fatty acid metal salt particles as the external additive,
  • the glass transition temperature (Tg) specified from the temperature dependence curve of the loss tangent (tan ⁇ ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz is 65.0° C. ⁇ Tg (° C.) ⁇ 75.0 fill °C, In the temperature dependence curve of the loss tangent (tan ⁇ ), when the loss tangent (tan ⁇ ) at Tg is tan ⁇ (Tg) and the loss tangent (tan ⁇ ) at 100 ° C.
  • the ratio of the blow-off charge amount of the toner after the stirring time of 1800 seconds to the blow-off charge amount of the toner after the stirring time of 180 seconds, measured by the charge amount measurement method described later, is 0.50 or more and 1.00 or less.
  • the second toner of the present disclosure has a glass transition temperature (Tg) of 65.0° C. or higher and 75.0° C. or lower, which is specified from the temperature dependence curve of the loss tangent (tan ⁇ ), and has a loss tangent (tan ⁇ ) of
  • Tg glass transition temperature
  • the toner has a specific viscoelasticity in which the area of the trapezoid specified from the temperature dependence curve is 35.0 or more and 48.0 or less, and the charge amount of the toner is measured by a specific charge amount measurement method described later.
  • the ratio (1800s/180s) is 0.50 or more and 1.00 or less, both low-temperature fixability and storage stability are improved in a well-balanced manner, and blowout is suppressed during durability under high-temperature and high-humidity conditions.
  • This toner has excellent performance that has been difficult to achieve in the past.
  • the ratio of the blow-off charge amount of the toner after the stirring time of 1800 seconds to the blow-off charge amount of the toner after the stirring time of 180 seconds, which is measured by a specific charge amount measurement method described later is referred to as the charge amount ratio ( 1800s/180s).
  • the ejection of toner is caused, for example, by local application of heat due to the sliding of the developing roller to the toner that has accumulated near the blade portion or seal portion of the cartridge, causing the accumulated toner to fuse and form aggregates. It occurs when the aggregate melts and the toner spills from the developing roller, or when the toner is not carried on the developing roller due to a decrease in the charge amount of the toner during running, and the toner leaks. In high-temperature and high-humidity environments, the charge amount of the toner itself tends to decrease, and the fluidity of the toner tends to decrease due to the moisture absorption of the toner. easier to do.
  • toner does not suddenly deform when it reaches a certain temperature during fixing and storage, but gradually deforms as the temperature rises or as time elapses when held at a certain temperature. .
  • the present inventors have found that the toner has a good balance between low-temperature fixability and storage stability, and the characteristics of the toner that easily suppresses the occurrence of blowout are identified from the temperature-tan ⁇ curve.
  • the charge amount ratio (1800s/180s) of the toner measured by a specific method, it was found that the toner appeared in the temperature (Tg) and the area of the trapezoid, and furthermore, the toner was maintained even during high temperature and high humidity durability.
  • the blowout can be suppressed.
  • the charge amount ratio (1800 s/180 s) can be used as an index of charge stability during durability of the toner. The closer the charge amount ratio (1800 s/180 s) is to 1.00, the better the charging stability of the toner during running.
  • the charge amount ratio (1800s/180s) is 0.50 or more and 1.00 or less, the decrease in the charge amount of the toner during running is sufficiently suppressed, and the toner needs to be carried on the developing roller. Since the charge amount can be maintained, the ejection of toner is suppressed.
  • the Tg specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz and the area of the trapezoid are within the specified ranges, and the charge amount ratio (1800 s/180 s) is as described above.
  • the toner has an excellent balance of low-temperature fixability and storage stability, and because the toner does not easily aggregate and the charge amount of the toner does not easily decrease during running, the ejection of toner during running is significantly suppressed. Therefore, it is possible to suppress the occurrence of toner ejection even during endurance under high temperature and high humidity conditions.
  • the characteristics of the second toner of the present disclosure, the manufacturing method and colored resin particles of the colored resin particles used in the second toner of the present disclosure, the external additive and the external additive used in the second toner of the present disclosure are described.
  • the addition treatment method and the performance of the second toner of the present disclosure will be described in order.
  • the ratio of the blow-off charge amount of the toner after 1800 seconds of stirring time measured by the following charge amount measurement method to the blow-off charge amount of the toner after 180 seconds of stirring time measured by the following charge amount measurement method. (In the present disclosure, it may be referred to as a charge amount ratio (1800s/180s).) is 0.50 or more and 1.00 or less.
  • the inventors have found that when the charge amount ratio (1800s/180s) is 1.00 or less, the charge rising property is improved. If the charging rising property is insufficient, problems such as toner blowing-out tend to occur in the initial stage of printing. From the viewpoint of improving the charge rise property, the charge amount ratio (1800s/180s) is preferably 0.90 or less, more preferably 0.80 or less.
  • [Charge amount measurement method] 0.25 g of toner and 9.75 g of uncoated spherical Mn--Mg--Sr--Fe ferrite carrier having an average particle size of 60 ⁇ m were placed in a glass container having a volume of 30 cc (inner bottom diameter: 30 mm, height: 50 mm).
  • a roller stirrer is used for a predetermined time, that is, 180 seconds or 1800 seconds, and is stirred at 160 rpm for triboelectrification treatment, 0.2 g of the mixture of the toner after the triboelectrification treatment and the ferrite carrier was placed in a Faraday cage, and was blown off for 30 seconds at a nitrogen gas pressure of 0.098 MPa using a blow-off powder charge amount measuring device. The blow-off charge amount ( ⁇ C/g) of the toner is measured.
  • the blow-off charge amount ( ⁇ C/g) of the toner can be calculated by the following formula (1).
  • Blow-off charge amount of toner ( ⁇ C/g) blow-off charge amount of mixture ( ⁇ C)/ ⁇ weight of mixture (0.2 g) ⁇ toner content in mixture (2.5%) ⁇
  • ferrite carrier used in the charge amount measurement method for example, a standard carrier EF-60 (: trade name, manufactured by Powdertech Co., Ltd., Mn-Mg-Sr-Fe system, spherical, no resin coating, average particle size 60 ⁇ m) can be used.
  • a blow-off powder charge amount measuring device used in the charge amount measurement method for example, a blow-off type Q/M meter (trade name, manufactured by Trek Japan) can be used.
  • the toner of the present disclosure preferably has a blow-off charge amount of 20 ⁇ C/g or more after 1800 seconds of agitation, which is measured by the charge amount measurement method, from the viewpoint of suppressing toner ejection during durability under high temperature and high humidity conditions. , more preferably 25 ⁇ C/g or more.
  • the upper limit of the blow-off charge amount is not particularly limited, it is preferably 40 ⁇ C/g or less, more preferably 35 ⁇ C/g or less, from the viewpoint of optimizing the image density.
  • the toner of the present disclosure having the properties described above can be obtained by adjusting the composition, molecular weight and content of the binder resin contained in the toner, the type and content of the external additive, and the toner production conditions such as external additive treatment conditions. You can get it by adjusting.
  • the viscoelasticity of the toner can be controlled mainly by the composition, molecular weight and content of the binder resin and the type and content of the external additive.
  • the charge ratio (1800s/180s) of the toner can be controlled mainly by adjusting the type and amount of the external additive, and can also be controlled by adding a polar resin to the colored resin particles. .
  • the colored resin particles used in the second toner of the present disclosure are produced by a wet method or a dry method in the same manner as the colored resin particles used in the first toner of the present disclosure. It can be produced, preferably by a wet method, and can be produced by adopting a particularly preferred suspension polymerization method among the wet methods.
  • a method for producing the colored resin particles used in the toner of the second aspect of the present disclosure by suspension polymerization method is generally the same as the method described in the first aspect of the present disclosure. Differences from the first aspect of the present disclosure will be described below.
  • the content of the polymerizable monomer used in “(A-1) the step of preparing the polymerizable monomer composition” is appropriately adjusted so that the toner has the specific viscoelasticity.
  • it is preferably 70 to 99 parts by mass, more preferably 75 to 97 parts by mass, and still more preferably 80 to 95 parts by mass with respect to 100 parts by mass of the total solid content contained in the polymerizable monomer composition. part by mass.
  • examples of the colorant used in "(A-1) the step of preparing a polymerizable monomer composition” include those similar to those in the first present disclosure.
  • Carbon black is preferable as the black colorant because it is easy to obtain a toner having a viscoelasticity of .
  • cyan colorant phthalocyanine pigments such as copper phthalocyanine pigments and derivatives thereof are preferred. I. Pigment Blue 15:3 is particularly preferred.
  • azo pigments such as disazo pigments are preferred, and among them C.I. I. Pigment Yellow 155 is particularly preferred.
  • condensed polycyclic pigments such as quinacridone pigments are preferred, and C.I. I. Pigment Red 122 is particularly preferred.
  • the content of the colorant is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 7 to 13 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomers. part by mass.
  • the content of the colorant is within the above range, it is easy to obtain the toner having the specific viscoelasticity.
  • examples of the charge control agent used in "(A-1) the step of preparing a polymerizable monomer composition” include those similar to those in the first aspect of the present disclosure. It has high compatibility with the organic monomer, can impart stable chargeability (charging stability) to the toner particles, and easily obtains a toner having a desired charge amount ratio (1800s/180s). A positively or negatively chargeable charge control resin is preferred.
  • Examples of the positively chargeable or negatively chargeable charge control resin include the same ones as in the first disclosure, and those preferably used in the first disclosure are also used in the second disclosure. It can be preferably used.
  • the above-mentioned functional group-containing copolymer used as a positively or negatively chargeable charge control resin among others, has the above functional group-containing copolymer because it is easy to obtain a toner having the specific viscoelasticity.
  • the proportion of group-containing structural units is preferably 10% by mass or less, more preferably 8% by mass or less.
  • the ratio of the functional group-containing structural unit in the functional group-containing copolymer is It is preferably 1.0% by mass or more, more preferably 3.0% by mass or more.
  • the charge control resin contains sufficient functional groups, the charge control resin is easily localized in the vicinity of the surface of the colored resin particles, and the charge control resin functions like a shell of the colored resin particles, thereby forming a toner. It is presumed that the charging stability and storage stability of the toner are improved, and the occurrence of blowout during durability under high temperature and high humidity is suppressed.
  • the charge control resin is usually 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, more preferably 0.6 to 10 parts by mass with respect to 100 parts by mass of the monovinyl monomer. It is used at a rate of 1.5 parts by mass.
  • the content of the charge control resin is equal to or higher than the above lower limit, the occurrence of fogging can be suppressed. can be done. Further, when the content of the charge control resin is within the above range, a toner having a desired charge amount ratio (1800s/180s) can be easily obtained.
  • the content of the charge control agent other than the charge control resin is preferably 10 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the charge control resin. is 5 parts by mass or less.
  • examples of the molecular weight modifier used in "(A-1) step of preparing a polymerizable monomer composition” include those similar to those in the first aspect of the present disclosure.
  • the content of the molecular weight modifier is adjusted so that the weight-average molecular weight Mw of the polymer contained in the binder resin is preferably A range is preferred.
  • the molecular weight modifier is preferably used in a proportion of 1.0 to 3.0 parts by weight, more preferably 1.1 to 2.0 parts by weight, per 100 parts by weight of the monovinyl monomer. As the content of the molecular weight modifier increases, the weight average molecular weight of the polymer contained in the binder resin tends to decrease.
  • the polymerizable monomer composition may contain a polar resin.
  • a polar resin By including a polar resin in the polymerizable monomer composition, the charge amount ratio (1800s/180s) of the toner can be adjusted, making it easier to control the particle size of the colored resin particles.
  • polar resins are selected from the group consisting of polymers containing repeating units containing heteroatoms. Specific examples of the polar resin include acrylic resins, polyester resins, vinyl resins containing heteroatoms, and the like.
  • the polar resin may be a homopolymer or copolymer of a heteroatom-containing monomer, or a copolymer of a heteroatom-containing monomer and a heteroatom-free monomer. .
  • the proportion of the heteroatom-containing monomer unit in 100% by mass of all repeating units constituting the copolymer is preferably 50% by mass or more, more preferably 70% by mass. or more, more preferably 90% by mass or more.
  • heteroatom-containing monomers used in the polar resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • heteroatom-free monomers used in the polar resin include heteroatom-free aromatic vinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, and p-methylstyrene; ethylene, propylene, monoolefin monomers such as butylene; and diene monomers such as butadiene and isoprene. These heteroatom-free monomers may be used alone or in combination of two or more.
  • the heteroatom-containing monomer contains a polar group containing at least one polar group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, a polyoxyethylene group and an epoxy group. Containing a monomer unit is preferable from the viewpoint that a toner having a desired charge amount ratio (1800s/180s) can be easily obtained and the particle size of the colored resin particles can be easily controlled. At least one selected from a carboxyl group and a hydroxyl group is preferable as the polar group.
  • polar group-containing monomers examples include carboxyl monomers such as ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid, and butentricarboxylic acid.
  • carboxyl monomers such as ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid, and butentricarboxylic acid.
  • Group-containing monomer hydroxyl group-containing monomer such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; sulfonic acid group-containing such as styrenesulfonic acid Monomers; amino group-containing monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate; polyoxyethylene group-containing monomers such as methoxypolyethylene glycol (meth)acrylate; glycidyl (meth)acrylate , allyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and other epoxy group-containing monomers.
  • hydroxyl group-containing monomer such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate
  • sulfonic acid group-containing such
  • polar group-containing monomers can be used either alone or in combination of two or more.
  • the polar resin contains a polar group-containing monomer unit
  • the polar group is located at the end of the main chain or side chain, or is attached to the main chain or side chain in a pendant form. is easily arranged on the surface of the droplets of the polymerizable monomer composition, a toner having a desired charge ratio (1800s/180s) is easily obtained, and the particle size of the colored resin particles is easily controlled.
  • the heteroatom-containing monomer unit contained in the polar resin has high compatibility with the polymerizable monomer, and the desired chargeability
  • a monomer unit derived from an alkyl (meth)acrylate is included in the point that a toner having an amount ratio (1800s/180s) can be easily obtained and the particle size of the colored resin particles can be easily controlled.
  • the alkyl group contains a monomer unit derived from an alkyl (meth) acrylate having 3 or less carbon atoms, and at least one selected from methyl (meth) acrylate and ethyl (meth) acrylate. It is more preferable to contain a monomer unit derived from, and it is still more preferable to contain a monomer unit derived from methyl (meth)acrylate.
  • the compatibility with the polymerizable monomer is high and a toner having a desired charge amount ratio (1800s/180s) can be easily obtained, and the particle size of the colored resin particles is controlled. From the viewpoint of ease of A copolymer with is more preferable.
  • such a copolymer of (meth)acrylic acid ester and (meth)acrylic acid may be referred to as an acrylic copolymer.
  • examples of the (meth)acrylic acid ester include those similar to the (meth)acrylic acid ester used for the heteroatom-containing monomer.
  • the (meth)acrylic acid ester may or may not contain the polar group, but preferably does not contain the polar group.
  • (Meth)acrylates are preferred.
  • the acrylic acid ester used in the acrylic copolymer is preferably at least one selected from the group consisting of ethyl acrylate, n-propyl acrylate, isopropyl acrylate and n-butyl acrylate, more preferably It is at least one selected from ethyl acrylate and n-butyl methacrylate.
  • the methacrylic acid ester used in the acrylic copolymer is preferably at least one selected from the group consisting of methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate and n-butyl methacrylate, more preferably It is methyl methacrylate.
  • the compatibility with the polymerizable monomer is high, a toner having a desired charge amount ratio (1800s/180s) can be easily obtained, and the particle size of the colored resin particles can be controlled.
  • the ratio of (meth)acrylic acid to 100% by mass of the total amount of (meth)acrylic acid ester and (meth)acrylic acid used in the synthesis of the acrylic copolymer is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.6% by mass, still more preferably 0.3 to 0.5% by mass.
  • the acrylic copolymer has a high compatibility with the polymerizable monomer, is easy to obtain a toner having a desired charge amount ratio (1800s/180s), and controls the particle size of the colored resin particles. From the viewpoint of ease of use, it is preferable to use a copolymer of monomers containing 50.0% by mass or more of methyl methacrylate with respect to 100% by mass of the total mass of monomers used in the synthesis of the copolymer.
  • the acrylic copolymer is more preferably a copolymer of monomers containing 50.0 to 99.9% by mass of methyl methacrylate and 0.1 to 5.0% by mass of (meth)acrylic acid.
  • a copolymer of monomers containing 50.0 to 99.0% by mass of methyl methacrylate and 0.1 to 5.0% by mass of (meth)acrylic acid still more preferably , 50.0 to 98.0% by mass of methyl methacrylate, 1.0 to 5.0% by mass of alkyl (meth)acrylate different from methyl methacrylate, and 0.1 to 5.0% by mass of (meth)acrylic acid
  • Particularly preferably, 50.0 to 98.0% by mass of methyl methacrylate and 1.0 to 5.0% by mass of alkyl (meth)acrylate different from methyl methacrylate It is a copolymer of monomers containing 0.2 to 3.0 mass of (meth)acrylic acid.
  • the alkyl (meth)acrylate different from methyl methacrylate at least one selected from ethyl acrylate and butyl acrylate is preferable because the glass transition point can be controlled.
  • the acrylic copolymer may contain a small amount of monomer units derived from other monomers different from both the (meth)acrylic acid ester and the (meth)acrylic acid.
  • the content of the other monomers is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 100% by mass of the total amount of monomers used in the synthesis of the acrylic copolymer. Most preferably, it is 10% by mass or less and does not contain the other monomers.
  • the acid value of the polar resin is preferably 0.5 to 7.0 mgKOH/g, more preferably 1.0 to 5.0 mgKOH/g, still more preferably 1.5 to 3.0 mgKOH/g. be.
  • the acid value of the polar resin is equal to or higher than the lower limit, heat-resistant storage stability, low-temperature fixability, and printing durability of the toner can be improved.
  • the acid value of the polar resin is equal to or less than the upper limit, the particle size of the colored resin particles can be easily controlled.
  • the acid value is a value measured in accordance with JIS K 0070, which is a standard fats and oils analysis method established by the Japan Industrial Standards Committee (JICS).
  • the weight average molecular weight (Mw) of the polar resin is preferably 8,000 to 45,000, more preferably 9,000 to 45,000, still more preferably 10,000 to 40,000.
  • the weight-average molecular weight (Mw) of the polar resin is at least the lower limit, the heat-resistant storage stability and durability of the toner can be improved, and when it is at most the upper limit, the fixing temperature of the toner increases. can be suppressed.
  • the weight average molecular weight (Mw) of the polymer can be determined by polystyrene conversion by GPC using a sample dissolved in tetrahydrofuran (THF).
  • the glass transition temperature (Tg) of the polar resin is preferably 60 to 95°C, more preferably 65 to 90°C, still more preferably 70 to 80°C.
  • the glass transition temperature Tg of the polar resin can be determined, for example, according to ASTM D3418-82.
  • the sample was heated at a heating rate of 10 ° C./min, and the maximum thermal peak of the DSC curve obtained in the process was measured.
  • the indicated temperature can be taken as the glass transition temperature.
  • polar resins can also be used. It can be produced by polymerizing by a known method such as a method. Further, when the polar resin is a copolymer, the copolymer may be a random copolymer, a block copolymer or a graft copolymer. preferable. Moreover, the polar resin is preferably pulverized more finely from the viewpoint of improving the solubility.
  • the content of the polar resin is preferably 0.8 to 2.5 parts by mass, more preferably 1.0 to 2.0 parts by mass, relative to 100 parts by mass of the polymerizable monomer. is.
  • the content of the polar resin is at least the lower limit, a toner having a desired charge ratio (1800s/180s) can be easily obtained, and the particle size of the colored resin particles can be easily controlled.
  • the content of the polar resin is equal to or less than the upper limit, it is possible to suppress an increase in the fixing temperature of the toner.
  • Colored Resin Particles Colored resin particles are obtained by the production method such as (A) the suspension polymerization method or (B) the pulverization method described above.
  • the colored resin particles contained in the second toner of the present disclosure are described below.
  • the colored resin particles described below include both core-shell type and non-core-shell type.
  • the colored resin particles used in the second disclosure contain a binder resin, a colorant, a softening agent and a charge control agent, and may further contain other additives as necessary.
  • the binder resin contained in the colored resin particles for example, the polymerizable monomers listed in the above-mentioned (A) suspension polymerization method (including the content cited from the first disclosure; the same shall apply hereinafter) are used. Examples thereof include polymers obtained by polymerization. Preferred polymerizable monomers from which each structural unit of the polymer is derived are the same as the preferred polymerizable monomers described in the above (A) suspension polymerization method.
  • the composition, weight-average molecular weight Mw, and content of the binder resin contained in the colored resin particles are the same as in the first disclosure.
  • the coloring agent, softening agent, and charge control agent contained in the colored resin particles are the same as those listed in (A) the suspension polymerization method (including the content of the first disclosure).
  • the content of the coloring agent and the content of the softening agent contained in the colored resin particles are the same as in the first aspect of the present disclosure.
  • the content of the charge control resin contained in the colored resin particles is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 10 parts by mass, with respect to 100 parts by mass of the binder resin. 5 parts by mass, more preferably 0.6 to 1.5 parts by mass.
  • the content of the charge control resin is equal to or higher than the lower limit, it is possible to suppress the occurrence of fogging. Further, when the content of the charge control resin is within the above range, a toner having a desired charge amount ratio (1800s/180s) can be easily obtained.
  • the second toner of the present disclosure contains the colored resin particles and an external additive.
  • the external additive can be adhered to the surface of the colored resin particles to form a one-component toner (developer).
  • the one-component toner may be further mixed and stirred with carrier particles to form a two-component developer, but the toner of the present disclosure is used as a one-component toner because the effects of the present disclosure are easily obtained. is preferred.
  • the toner of the present disclosure is preferably a non-magnetic toner containing no magnetic powder, and more preferably a non-magnetic one-component toner.
  • the second toner of the present disclosure contains fatty acid metal salt particles as an external additive.
  • the toner having the specific viscoelasticity and desired charge ratio (1800s/180s) can be easily obtained.
  • the charge amount ratio (1800s/180s) of the toner can be set to 0.50 to 1.00 by using silicone resin particles as an external additive.
  • the adhesion of the toner is low when the toner moves from the photoreceptor to the paper, causing the toner to scatter.
  • density unevenness may occur in the formed image.
  • the toner of the present disclosure uses fatty acid metal salt particles as an external additive and has a charge amount ratio (1800s/180s) of 0.50 to 1.00. is less likely to occur.
  • fatty acid metal salt particles can improve the charging stability of the toner with a smaller addition amount.
  • the amount of the external additive is too large, the toner tends to deteriorate in low-temperature fixability. can be suppressed.
  • the fatty acid metal salt particles are rubbed and spread over the toner particles or the entire system in the printer during endurance, thereby improving the charging stability of the toner.
  • the number average primary particle size is preferably 1.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, because the above effects of the fatty acid metal salt particles are likely to be effectively exhibited.
  • the lower limit of the content of the fatty acid metal salt particles is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and still more preferably 100 parts by mass of the binder resin in the colored resin particles. It is 0.03 parts by mass or more, more preferably 0.04 parts by mass or more, and the upper limit is preferably 0.19 parts by mass or less, more preferably 0.17 parts by mass or less, and still more preferably 0.15 parts by mass. parts or less, more preferably 0.13 parts by mass or less.
  • the charge ratio (1800s/180s) of the toner tends to be at least 0.50, charging stability during running is improved, and high temperature and high humidity conditions are achieved.
  • the fatty acid moiety (R—COO ⁇ ) possessed by the fatty acid metal salt particles used in the toner of the second present disclosure and the metal contained in the fatty acid metal salt particles are the same as those of the first present disclosure.
  • commercial products of the fatty acid metal salt particles used in the toner of the second aspect of the present disclosure include those similar to those of the first aspect of the present disclosure.
  • inorganic fine particles A having a number average primary particle size of 36 to 100 nm it is preferable to further contain inorganic fine particles A having a number average primary particle size of 36 to 100 nm as an external additive. If the number average primary particle diameter of the inorganic fine particles A is less than 36 nm, the charge amount ratio (1800s/180s) may be less than 0.50, and the spacer effect may be reduced, resulting in printing problems such as fogging. Performance may be adversely affected. On the other hand, when the number average primary particle diameter of the inorganic fine particles A exceeds 100 nm, the charge amount ratio (1800s/180s) may be less than 0.50. is likely to be liberated, and the function as an external additive may deteriorate, adversely affecting printing performance.
  • the number average primary particle diameter of the inorganic fine particles A is more preferably 40 nm or more, still more preferably 45 nm as a lower limit, and more preferably 80 nm or less, still more preferably 70 nm or less as an upper limit. Further, the inorganic fine particles A are preferably subjected to a hydrophobic treatment.
  • silane coupling agents, silicone oils, fatty acids and fatty acid metal salts can be used as hydrophobizing agents. Among these, silane coupling agents and silicone oils are preferred.
  • the lower limit of the content of the inorganic fine particles A is preferably 0.30 parts by mass or more, more preferably 0.50 parts by mass or more, and still more preferably 1 part by mass with respect to 100 parts by mass of the binder resin in the colored resin particles. 00 parts by mass or more, and the upper limit is preferably 2.50 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.50 parts by mass or less.
  • the content of the inorganic fine particles A is at least the above lower limit, the function as an external additive can be sufficiently exerted, so deterioration of printing performance or storage stability is suppressed.
  • the content of the inorganic fine particles A is equal to or less than the above upper limit, separation of the inorganic fine particles A from the surface of the toner particles is suppressed, thereby suppressing deterioration of printing performance.
  • inorganic fine particles B having a number average primary particle size of 15 to 35 nm as an external additive. If the number average primary particle size of the inorganic fine particles B is less than 15 nm, the charge amount ratio (1800s/180s) may be less than 0.50, and printing performance may be adversely affected. On the other hand, when the number-average primary particle diameter of the inorganic fine particles B exceeds 35 nm, the charge amount ratio (1800s/180s) may be less than 0.50. Since the proportion (coverage) of B is lowered, it may not be possible to impart sufficient fluidity to the toner particles.
  • the lower limit of the number average primary particle diameter of the inorganic fine particles B is more preferably 17 nm or more, more preferably 20 nm or more, and the upper limit is more preferably 30 nm or less, still more preferably 25 nm or less. Moreover, it is preferable that the inorganic fine particles B are subjected to a hydrophobic treatment.
  • the lower limit of the content of the inorganic fine particles B is preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, and still more preferably 0 parts by mass with respect to 100 parts by mass of the binder resin in the colored resin particles.
  • the upper limit is preferably 2.00 parts by mass or less, more preferably 1.50 parts by mass or less, and even more preferably 1.00 parts by mass or less.
  • the content of the inorganic fine particles B is equal to or less than the above upper limit, the release of the inorganic fine particles B from the surface of the toner particles is suppressed, thereby suppressing the deterioration of the charging characteristics and thus suppressing the occurrence of fogging. be done.
  • inorganic fine particles C having a number average primary particle diameter of 6 to 14 nm as an external additive. If the number average primary particle size of the inorganic fine particles C is less than 6 nm, the charge amount ratio (1800s/180s) may be less than 0.50, and printing performance may be adversely affected. On the other hand, when the number-average primary particle diameter of the inorganic fine particles C exceeds 14 nm, the charge amount ratio (1800s/180s) may be less than 0.50. Since the proportion (coverage) of C is lowered, sufficient fluidity may not be imparted to the toner particles in some cases.
  • the number average primary particle diameter of the inorganic fine particles C has a lower limit of preferably 6.5 nm or more, more preferably 7.0 nm or more, and an upper limit of more preferably 12 nm or less, still more preferably 10 nm or less. Moreover, the inorganic fine particles C are preferably subjected to a hydrophobic treatment.
  • the lower limit of the content of the inorganic fine particles C is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, and still more preferably 0 parts by mass with respect to 100 parts by mass of the binder resin in the colored resin particles. .20 parts by mass or more, and the upper limit is preferably 1.50 parts by mass or less, more preferably 1.00 parts by mass or less, still more preferably 0.80 parts by mass or less, and even more preferably 0.60 parts by mass. It is below.
  • the content of the inorganic fine particles C is at least the above upper limit, the function as an external additive can be sufficiently exerted, thereby suppressing deterioration of fluidity and deterioration of storage stability.
  • the content of the inorganic fine particles C is equal to or less than the above upper limit, the release of the inorganic fine particles C from the surface of the toner particles is suppressed, thereby suppressing the deterioration of the charging characteristics and thus causing fogging. Suppressed.
  • the second toner of the present disclosure preferably contains any one of the inorganic fine particles A to C, more preferably any two, and even more preferably all three.
  • the viscoelasticity, fluidity, fixability, preservability, charging stability, etc. of the toner can be adjusted by appropriately adjusting the particle size and the amount of addition of the inorganic fine particles A to C.
  • inorganic fine particles A, B and C examples of inorganic fine particles A, B and C and descriptions of commercial products are the same as in the first disclosure.
  • the second toner of the present disclosure contains, as an external additive, fatty acid metal salt particles and at least one selected from the group consisting of the inorganic fine particles A, B, and C described above in combination. It is preferable from the viewpoint that the stability is improved and the effect of suppressing the toner ejection during durability under high temperature and high humidity is improved. Since the fatty acid metal salt particles can function as a binder for the secondary particles of the inorganic fine particles A, B, or C, by including these in combination, the secondary particles of the inorganic fine particles A, B, or C can be retained even during durability. is maintained, and it is presumed that a high charge amount can be maintained.
  • the second toner of the present disclosure may contain other external additives different from the fatty acid metal salt particles and inorganic fine particles A to C described above within a range that does not impair the effects of the present disclosure.
  • the content of the other external additive is preferably 10 parts by mass or less, more preferably 5 parts by mass or less in 100 parts by mass of the external additive. Thereby, the occurrence of density unevenness can be suppressed. From the viewpoint of suppressing density unevenness, it is particularly preferable that the content of the silicone resin particles is equal to or less than the above upper limit.
  • a known external addition treatment method can be employed, and is not particularly limited, but in the second aspect of the present disclosure, the addition Part of the external additive is mixed with the colored resin particles in a wet state, stirred, and dried to obtain intermediate particles.
  • a method of performing a second-stage external addition treatment of mixing and stirring is preferred.
  • the external addition treatment is performed in two stages in this manner, the external additive added before drying the colored resin particles becomes relatively easily embedded in the surface of the colored resin particles, and is added after drying the colored resin particles.
  • the added external additive becomes relatively difficult to embed in the surface of the colored resin particles. As a result, unevenness on the surface of the toner particles becomes appropriate, so that low-temperature fixability and storage stability can be improved in a well-balanced manner.
  • the wet colored resin particles used in the first-stage external addition treatment preferably have a moisture content of 5 to 20%, more preferably 6 to 15%, and even more preferably 7 to 12%.
  • the intermediate particles used in the second-stage external addition treatment preferably have a moisture content of 1% or less, more preferably 0.8% or less, and even more preferably 0.5% or less.
  • the external additive added in the external addition treatment in the first stage preferably contains the inorganic fine particles C, and more preferably consists of the inorganic fine particles C described above.
  • the external additive added in the second-stage external addition treatment preferably contains the fatty acid metal salt particles, and more preferably contains the fatty acid metal salt particles and the inorganic fine particles A and B.
  • first-stage external addition treatment method and the second-stage external addition treatment method is the same as in the first disclosure.
  • the peripheral speed of the stirring blade during the external addition treatment is preferably 35 to 55 m/s, more preferably 40 to 50 m/s, in order to easily obtain the second toner of the present disclosure.
  • the time for the external addition treatment is preferably 6 minutes to 15 minutes, more preferably 6 minutes to 12 minutes.
  • the conditions for mixing and stirring in the first stage of the external addition treatment are not particularly limited.
  • the stirring time can be from 10 hours to 48 hours.
  • the second toner of the present disclosure preferably has a volume average particle diameter (Dv) of 3 to 15 ⁇ m, more preferably 4 to 12 ⁇ m.
  • Dv volume average particle diameter
  • the Dv of the toner is equal to or higher than the above lower limit, the fluidity of the toner can be improved, the deterioration of the transferability and the reduction of the image density can be suppressed, and the occurrence of the toner blowing out can be suppressed during endurance under high temperature and high humidity conditions. can do.
  • the Dv of the toner is equal to or less than the above upper limit, it is possible to suppress the deterioration of image resolution.
  • the ratio (Dv/Dn) of the volume-average particle diameter (Dv) to the number-average particle diameter (Dn) is preferably 1.0 to 1.3. is preferably 1.0 to 1.2.
  • the volume average particle diameter and number average particle diameter of the toner can be measured using, for example, a particle size analyzer (manufactured by Beckman Coulter, trade name: Multisizer).
  • the average circularity of the second toner of the present disclosure is preferably 0.96 to 1.00, more preferably 0.97 to 1.00, and 0.98. ⁇ 1.00 is more preferred.
  • the degree of circularity of the toner is determined, for example, by using an aqueous solution in which the toner is dispersed as a sample liquid, and measuring the number of toner particles in the sample liquid using a flow-type particle image analyzer (for example, Simex Co., Ltd., trade name: FPIA-2100, etc.).
  • a projected image is photographed, and from the projected image, the perimeter of a circle equal to the projected area of the toner particles and the perimeter of the projected image of the toner particles are measured. can be obtained by dividing the perimeter of a circle equal to )/(the perimeter of the projected particle image).
  • the average circularity is the average circularity of each toner particle contained in the sample liquid.
  • the volume average particle diameter (Dv), number average particle diameter (Dn), and average circularity of the toner do not show significant differences depending on the presence or absence of the external additive.
  • Colored resin particles containing no additive can be considered to have the same volume average particle size (Dv), number average particle size (Dn) and average circularity.
  • the second toner according to the present disclosure is one in which the occurrence of blowout during endurance under high temperature and high humidity is suppressed.
  • the second toner of the present disclosure was left for 24 hours in a high temperature and high humidity environment, and after an endurance test in which 5,000 sheets were continuously printed at a print density of 5% in the same environment, the toner escaped from the developing roller of the cartridge. It is preferable that the toner does not spill, and more preferably, the toner only spills from a part of the developing roller or does not spill from the developing roller when the cartridge is further tilted after the endurance test.
  • the description of the blowout test during endurance of toner under high temperature and high humidity is the same as in the first disclosure.
  • the second toner of the present disclosure has good storability and suppresses a decrease in blocking occurrence temperature (heat resistant temperature).
  • the second toner of the present disclosure has a blocking temperature (heat resistant temperature) of preferably 54° C. or higher, more preferably 55° C. or higher, and even more preferably 56° C. or higher.
  • the definition of the blocking occurrence temperature and the description of the measuring method are the same as in the first disclosure.
  • the second toner of the present disclosure has good low-temperature fixability.
  • a solid image is printed on paper using a printer at a fixing roll temperature of 150° C., and the density reduction rate when a rubbing test is performed on the solid area.
  • it is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less.
  • the explanation of how to obtain the density decrease rate is the same as in the first disclosure.
  • Example I series examples relating to the toner of the first disclosure
  • Example II series examples relating to the toner of the second disclosure
  • the present disclosure is limited only to these examples. not something. Parts and % are based on mass unless otherwise specified.
  • the weight average molecular weight Mw of the polymer was determined by polystyrene conversion by GPC. A sample for measurement was prepared by dissolving the polymer in tetrahydrofuran (THF) to a concentration of 2 mg/mL, sonicating the solution for 10 minutes, and passing it through a 0.45 ⁇ m membrane filter.
  • THF tetrahydrofuran
  • the measurement conditions were temperature: 40°C, solvent: tetrahydrofuran, flow rate: 1.0 mL/min, concentration: 0.2 wt%, sample injection volume: 100 ⁇ L. 30 cm x 2) were used.
  • the measurement was performed under the condition that the first-order correlation of Log (Mw)-elution time between weight average molecular weights Mw of 1,000 to 300,000 was 0.98 or more.
  • the weight-average molecular weight Mw of the polymer contained in the binder resin in the toner was obtained by using a sample obtained by dissolving the toner in THF, and using the results of GPC obtained by the above-described measurement method.
  • the weight-average molecular weight Mw was determined using the data from which the resin and softener peaks were subtracted.
  • Table 1 for the numerical value of the weight average molecular weight Mw, the exponential notation defined in JIS X 0210 is used for simplification. For example, “5.04 ⁇ 10 5 " is written as "5.04E+05".
  • Example I-1 Production of colored resin particles 1-1.
  • Pigment Yellow 155 (trade name: Toner Yellow 3GP CT, manufactured by Clariant) was wet pulverized using a media-type dispersing machine (trade name: Picomil, manufactured by Asada Iron Works Co., Ltd.).
  • a charge control resin (a styrene acrylic resin containing a quaternary ammonium salt, manufactured by Fujikura Kasei Co., Ltd., trade name: Acrybase (registered trademark) FCA-161P, with a functional group content of 8% by mass) was added to the mixture obtained by the wet pulverization. 0.8 part and 6.0 parts of synthetic ester wax (pentaerythritol tetrabehenate, melting point 76° C.) were added, mixed and dissolved to prepare a polymerizable monomer composition for core.
  • synthetic ester wax penentaerythritol tetrabehenate, melting point 76° C.
  • aqueous dispersion medium On the other hand, to an aqueous solution of 10.4 parts of magnesium chloride dissolved in 280 parts of ion-exchanged water, an aqueous solution of 7.3 parts of sodium hydroxide dissolved in 50 parts of ion-exchanged water was gradually added with stirring to obtain a hydroxide solution. A magnesium colloidal dispersion was prepared.
  • Preparation of polymerizable monomer for shell On the other hand, 2 parts of methyl methacrylate and 130 parts of water were finely dispersed using an ultrasonic emulsifier to prepare an aqueous dispersion of a polymerizable monomer for shell.
  • Polymerization process A dispersion liquid containing droplets of the polymerizable monomer composition for the core was placed in a reactor, and the temperature was raised to 90° C. to carry out a polymerization reaction. After the polymerization conversion reached approximately 100%, 2,2′-azobis[2-methyl-N-(2-hydroxyethyl) was added as a shell polymerization initiator to the aqueous dispersion of the polymerizable monomer for shell. -propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble initiator) dissolved in 0.1 parts was added to the reactor. Then, the temperature was maintained at 95° C. for 4 hours to continue the polymerization, and then the reaction was stopped by cooling with water to obtain an aqueous dispersion of core-shell type colored resin particles.
  • -propionamide manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble initiator
  • washing, filtering and dehydration process While stirring the aqueous dispersion of the colored resin particles, sulfuric acid was added until the pH reached 4.5 or less for acid washing (25°C, 10 minutes). Wash and filter the wash water. The electrical conductivity of the filtrate at this time was 20 ⁇ S/cm. Further, the colored resin particles after washing and filtering were dehydrated to obtain colored resin particles in a wet state.
  • volume average particle size (Dv) About 0.1 g of the colored resin particles obtained in the above “1-6. Washing, filtering and dehydrating step” was weighed, placed in a beaker, and an aqueous surfactant solution (manufactured by FUJIFILM Corporation, trade name: Drywell) was used as a dispersant. 0.1 mL was added. 10 to 30 mL of Isoton II was further added to the beaker, dispersed for 3 minutes with a 20 W (Watt) ultrasonic disperser, and then a particle size measuring machine (manufactured by Beckman Coulter, trade name: Multisizer) was used. , aperture diameter: 100 ⁇ m, medium: Isoton II, number of measured particles: 100,000, the volume average particle diameter (Dv) of the colored resin particles was measured.
  • Toner 2-1 External additive treatment in the first stage: The wet colored resin particles obtained in the above “1-6. Washing, filtering and dehydrating step” were collected so that the content of the binder resin in the colored resin particles was 100 parts by mass. After adding 0.20 parts of hydrophobized silica fine particles (manufactured by Cabot Corporation, trade name: TG-820F) having a number average primary particle size of 7 nm as inorganic fine particles C to the collected wet colored resin particles, these are added.
  • hydrophobized silica fine particles manufactured by Cabot Corporation, trade name: TG-820F
  • Second-stage external addition treatment In the intermediate particles, 1.33 parts of hydrophobized silica fine particles (trade name: H05TA, manufactured by Clariant Co., Ltd.) having a number average primary particle size of 50 nm as inorganic fine particles A, and a number average primary particle size of 20 nm as inorganic fine particles B.
  • hydrophobized silica fine particles (trade name: H05TA, manufactured by Clariant Co., Ltd.) having a number average primary particle size of 50 nm as inorganic fine particles A, and a number average primary particle size of 20 nm as inorganic fine particles B.
  • hydrophobized silica fine particles manufactured by Cabot Corporation, product name: TG-7120
  • inorganic fine particles C hydrophobized silica fine particles having a number average primary particle diameter of 7 nm
  • fatty acid metal salt particles zinc stearate particles, manufactured by Sakai Chemical Industry Co., Ltd., trade name: SPZ-100F having a number average primary particle diameter of 0.5 ⁇ m as organic fine particles D.
  • Example I-1 was prepared by stirring.
  • Example I-2 In Example I-1, the procedure was the same as in Example I-1, except that the amount of the organic fine particles D (SPZ-100F) added in "2. Production of Toner” was changed according to Table 1 below. , to obtain the toner of Example I-2.
  • Example I-1 the amount of divinylbenzene (DVB) added during the above “1-1.
  • Preparation of polymerizable monomer composition for core in “1. Production of colored resin particles” Change according to Table 1, and add inorganic fine particles C (TG-820F) in the second stage external addition treatment without adding inorganic fine particles C (TG-820F) in the second stage external addition treatment in the above “2. Production of toner”. Toners of Examples I-3 to I-6 were obtained in the same manner as in Example I-1, except that the amount of each external additive added was changed according to Table 1 below.
  • Example I-7 In Example I-1, the type of colorant added during the above “1-1. Preparation of polymerizable monomer composition for core" in “1. Production of colored resin particles” was determined according to Table 1 below. A toner of Example I-7 was obtained in the same manner as in Example I-1 except for the change.
  • Example I-8 In Example I-1, the procedure was the same as in Example I-1, except that the type of organic fine particles D (fatty acid metal salt particles) added in "2. Production of toner” was changed according to Table 1 below. , to obtain the toner of Example I-8.
  • the type of organic fine particles D fatty acid metal salt particles
  • Example I-9 In Example I-1, the amount of divinylbenzene (DVB) added in the above "1. Production of colored resin particles” and “1-1. Preparation of polymerizable monomer composition for core”, and The addition amount of the charge control resin (Acrybase (registered trademark) FCA-161P) was changed according to Table 1 below, and in addition, in the second step of the external addition treatment in the above "2. Production of toner", inorganic fine particles C Example I was carried out in the same manner as in Example I-1, except that (TG-820F) was not added and the amount of each external additive added in the second stage of external addition treatment was changed according to Table 1 below. A -9 toner was obtained.
  • FCA-161P charge control resin
  • Example I was carried out in the same manner as in Example I-1, except that (TG-820F) was not added and the amount of each external additive added in the second stage of external addition treatment was changed according to Table 1 below. A -9 toner was obtained.
  • Comparative Example I-1 Comparative Example I-1 was prepared in the same manner as in Example I-1, except that the organic fine particles D (SPZ-100F) were not added in the above "2. Production of toner” in Example I-1. of toner.
  • Example I-2 In Example I-1, the materials used in “1-1. Preparation of polymerizable monomer composition for core” in “1. Production of colored resin particles” were changed according to Table 2 below. Furthermore, in the above “2. Production of toner”, the inorganic fine particles C (TG-820F) were not added in the external addition treatment in the second stage, and the amount of each external additive added was changed according to Table 2 below. A toner of Comparative Example I-2 was obtained in the same manner as in Example I-1 except for the above.
  • Example I-1 the materials used in “1-1. Preparation of polymerizable monomer composition for core” in “1. Production of colored resin particles” were changed according to Table 2 below. Furthermore, in the above “2. Production of toner”, in the external addition treatment of the first stage, only the colored resin particles are mixed, stirred and dried without adding the inorganic fine particles C (TG-820F).
  • Example I-1 except that the external additive added in the external addition treatment at the stage was changed according to Table 2 below, and the peripheral speed of the stirring blade and the external addition treatment time in the external addition treatment were changed according to Table 2 below. Toners of Comparative Examples I-3 to I-5 were obtained in the same manner as above.
  • a temperature dependence curve of loss tangent (tan ⁇ ) was obtained by dynamic viscoelasticity measurement.
  • Dynamic viscoelasticity was measured using a rotating plate rheometer (ARES-G2, manufactured by TA Instruments) using a crosshatch plate under the following conditions.
  • a test piece was prepared by pouring 0.2 g of toner into an 8 mm ⁇ cylindrical molding device and pressing the toner at 1.0 MPa for 30 seconds to form a cylindrical molding having a thickness of 3 mm and a diameter of 8 mm.
  • the linearity of the temperature dependence curve of the loss tangent (tan ⁇ ) of the toner obtained in each example is such that from 45° C. to the glass transition temperature (Tg) shown in Table 1, tan ⁇ changes from around 0 to 1 as the temperature rises. .8, tan ⁇ reaches a maximum value at Tg, and from Tg to around 100°C, tan ⁇ decreases as the temperature rises, and tan ⁇ becomes about 0.8 to 0.9 around 100°C. , tan ⁇ reaches a minimum value, and from the temperature at this minimum value to 190° C., tan ⁇ gradually increases with increasing temperature and then becomes a substantially constant value linearly.
  • Tg glass transition temperature
  • Example 1 shows the temperature dependence curve of the loss tangent (tan ⁇ ) of the toner obtained in Example I-1. Further, from the obtained temperature-tan ⁇ curve, the glass transition temperature (Tg) of each toner, the loss tangent tan ⁇ (Tg) at the glass transition temperature (Tg), and the loss tangent tan ⁇ (100° C.) at 100° C. are obtained. 100° C.) value as the upper base, the value of tan ⁇ (Tg) as the lower base, and the value of 100 ⁇ Tg as the height.
  • the trapezoid identified from the temperature-tan ⁇ curve shown in FIG. 1 is the trapezoid ABCD shown in FIG.
  • the point of tan ⁇ (100° C.) is defined as point A
  • the point of tan ⁇ (Tg) is defined as point B
  • the measurement container is set in an analyzer equipped with a propeller blade, the tip speed of the blade is set to 60 mm/sec, and the angle of approach of the blade is set to 5° clockwise.
  • the blade was passed through the inside of the toner layer from the surface and reached a position 10 mm from the bottom of the measurement container.
  • the blade was lowered to a position 1 mm from the bottom surface of the measuring container by changing the approach angle of the blade to 2° clockwise without changing the tip speed of the blade.
  • BET specific surface area was measured by a nitrogen adsorption method (BET method) using a fully automatic BET specific surface area measuring device (manufactured by Mountech, trade name: Macsorb HM model-1208).
  • the mass of the toner remaining on the sieve was measured and taken as the mass of aggregated toner.
  • the maximum temperature at which the mass of the aggregated toner becomes 0.5 g or less is defined as the heat resistance temperature of the toner. The higher the heat resistant temperature, the less likely the toner will be blocked during storage, and the better the storage stability.
  • Tables 1 and 2 The abbreviations in Tables 1 and 2 are as follows.
  • ST styrene BA: n-butyl acrylate
  • DVB divinylbenzene
  • TET Tetraethylthiuram disulfide 161P: Styrene acrylic resin containing quaternary ammonium salt, manufactured by Fujikura Kasei Co., Ltd., trade name: Acrybase FCA-161P, functional group content 8% by mass
  • PY155 C.I. I. pigment yellow 155 PB15:3: C.I. I.
  • TG820F Hydrophobized silica fine particles having a number average primary particle size of 7 nm (manufactured by Cabot, trade name: TG-820F)
  • TG7120 Hydrophobized silica fine particles having a number average primary particle size of 20 nm (manufactured by Cabot Corporation, trade name: TG-7120)
  • H05TA Hydrophobized silica fine particles having a number average primary particle size of 50 nm (manufactured by Clariant, trade name: H05TA)
  • SPZ-100F Fatty acid metal salt particles with a number average primary particle size of 0.5 ⁇ m (zinc stearate particles, manufactured by Sakai Chemical Industry Co., Ltd., trade name: SPZ-100F)
  • SPX-100F Fatty acid metal salt particles with a number average primary particle size of 0.72 ⁇ m (magnesium stearate particles, manufactured by Sakai Chemical Industry Co., Ltd., trade name
  • Comparative Example I-1 Since the toner of Comparative Example I-1 had a CBD exceeding 0.550 g/mL, the toner was ejected from the entire surface of the developing roller when the durability test was performed under high temperature and high humidity conditions.
  • the toner of Comparative Example I-2 had a Tg of more than 75.0° C. and an area of the trapezoid of less than 35.0. was inferior.
  • the toner of Comparative Example I-3 had a fluidity of less than 80%, the toner spurted out from the entire surface of the developing roller when the durability test was performed under high temperature and high humidity conditions.
  • Comparative Example I-3 is based on materials and procedures similar to Example I series of Patent Document 1.
  • the toner of Comparative Example I-4 had a Tg of more than 75.0° C., an area of the trapezoid of less than 35.0, and a flowability of less than 80%. In other words, the low-temperature fixability was poor, and when a durability test was conducted under high temperature and high humidity conditions, toner was ejected from a part of the developing roller.
  • Comparative Example I-4 is based on materials and procedures similar to those of the examples of Patent Document 2.
  • the toner of Comparative Example I-5 had a trapezoidal area of more than 48.0, a fluidity of less than 80%, and a CBD of less than 0.527 g/mL. Blocking during storage tends to occur, resulting in poor storage stability. Further, when a durability test was performed under high temperature and high humidity conditions, toner spurted out from the entire surface of the developing roller.
  • the toners of Examples I-1 to I-9 have a glass transition temperature (Tg) of 65.0° C. ⁇ Tg (° C.) ⁇ 75.0° C. specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz.
  • the area of the trapezoid is 35.0 or more and 48.0 or less, and the CBD is 0. 0.527 g/mL or more and 0.550 g/mL or less, and the fluidity was 80% or more, so that the heat resistance temperature is high, that is, the toner is less likely to be blocked during storage, so the storage stability is excellent, and the solid area is excellent.
  • the density decrease rate before and after the rubbing test is high, that is, the low-temperature fixability is excellent, and the toner does not blow out even when the durability test is performed under high temperature and high humidity. The toner was suppressed in ejection.
  • Example II-3 In Example II-3 (same as Example I-3), except that the fatty acid metal salt particles (SPZ-100F) were not added during the above "2. Production of toner", Example II-3 A toner of Comparative Example II-1 was obtained in the same manner as above.
  • Example II-2 In Example II-1 (same as Example I-1), used in the above “1-1. Preparation of polymerizable monomer composition for core” in “1. Production of colored resin particles” Each material was changed according to Table 3 below, and in addition, in the second stage of the external addition treatment in "2. Production of toner", inorganic fine particles C (TG-820F) were not added, and each external additive was added. A toner of Comparative Example II-2 was obtained in the same manner as in Example II-1 except that the amount added was changed according to Table 3 below.
  • Example II-3 In Example II-1 (same as Example I-1), used in the above “1-1. Preparation of polymerizable monomer composition for core” in "1. Production of colored resin particles” Each material was changed according to Table 3 below, and only colored resin particles were added without adding inorganic fine particles C (TG-820F) in the first stage of the external addition treatment in the above "2. Production of toner”. Mixing, stirring and drying were carried out at, except that the external additive added in the external addition treatment was changed according to Table 3 below, and the peripheral speed of the stirring blade and the external addition treatment time in the external addition treatment were changed according to Table 3 below. A toner of Comparative Example II-3 was obtained in the same manner as in Example II-1.
  • the glass transition temperature (Tg) of each toner, the loss tangent tan ⁇ (Tg) at the glass transition temperature (Tg), the loss tangent tan ⁇ at 100° C. (100° C.) was determined, and the area of a trapezoid was calculated with the value of tan ⁇ (100° C.) as the upper base, the value of tan ⁇ (Tg) as the lower base, and the value of 100 ⁇ Tg as the height.
  • the blow-off charge amount of the toner after the stirring time of 1800 seconds was repeated in the same manner as the above method except that the stirring time was changed from 180 seconds to 1800 seconds. asked for Then, the ratio of the blow-off charge amount of the toner after the stirring time of 1800 seconds to the blow-off charge amount of the toner after the stirring time of 180 seconds (charge amount ratio (1800 s/180 s)) was calculated.
  • volume average particle size (Dv) About 0.1 g of toner was weighed and placed in a beaker, and 0.1 mL of a surfactant aqueous solution (manufactured by Fuji Film Co., Ltd., trade name: DRYWELL) was added as a dispersant. 10 to 30 mL of Isoton II was further added to the beaker, dispersed for 3 minutes with a 20 W (Watt) ultrasonic disperser, and then a particle size measuring machine (manufactured by Beckman Coulter, trade name: Multisizer) was used. , aperture diameter: 100 ⁇ m, medium: Isoton II, number of measured particles: 100,000, the volume average particle diameter (Dv) of the toner was measured.
  • a surfactant aqueous solution manufactured by Fuji Film Co., Ltd., trade name: DRYWELL
  • the toner of Comparative Example II-1 did not contain fatty acid metal salt particles as an external additive and had a charge ratio (1800s/180s) of less than 0.50. Toner was ejected from the entire surface of the developing roller.
  • the toner of Comparative Example II-2 had a Tg of more than 75.0° C. and an area of the trapezoid of less than 35.0. was inferior.
  • the toner of Comparative Example II-3 had a trapezoidal area of more than 48.0, and therefore had a low heat resistance temperature. When the endurance test was performed in a humid environment, toner was ejected from the entire surface of the developing roller.
  • the toners of Examples II-1 to II-8 have a glass transition temperature (Tg) of 65.0° C. ⁇ Tg (° C.) ⁇ 75.0° C. specified from the temperature-tan ⁇ curve at a measurement frequency of 24 Hz.
  • Tg glass transition temperature
  • the area of a trapezoid with the value of tan ⁇ (100° C.) as the upper base, the value of tan ⁇ (Tg) as the lower base, and the value of 100 ⁇ Tg as the height is 35.0 or more and 48.0 or less, and the charge amount ratio Since (1800 s/180 s) was 0.50 or more and 1.00 or less, the heat resistance temperature is high, that is, the toner is less likely to be blocked during storage, so the storage stability is excellent.

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